TWI498156B - Pollutant Removal Agent, Carbon / Polymer Composites, Contaminants Removal of Plate Components and Filter - Google Patents

Pollutant Removal Agent, Carbon / Polymer Composites, Contaminants Removal of Plate Components and Filter Download PDF

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Publication number
TWI498156B
TWI498156B TW101104089A TW101104089A TWI498156B TW I498156 B TWI498156 B TW I498156B TW 101104089 A TW101104089 A TW 101104089A TW 101104089 A TW101104089 A TW 101104089A TW I498156 B TWI498156 B TW I498156B
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Taiwan
Prior art keywords
porous carbon
carbon material
pores
volume
surface area
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TW101104089A
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Chinese (zh)
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TW201238652A (en
Inventor
Shun Yamanoi
Hironori Iida
Machiko Minatoya
Seiichiro Tabata
Shinichiro Yamada
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Sony Corp
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Publication of TW201238652A publication Critical patent/TW201238652A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/04—Feed pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/08—Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28011—Other properties, e.g. density, crush strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
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    • B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28076—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being more than 1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28078—Pore diameter
    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/336—Preparation characterised by gaseous activating agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C02F1/003—Processes for the treatment of water whereby the filtration technique is of importance using household-type filters for producing potable water, e.g. pitchers, bottles, faucet mounted devices
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/00—Treatment of water, waste water, or sewage
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    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
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    • B01D2311/04—Specific process operations in the feed stream; Feed pretreatment
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/485—Plants or land vegetals, e.g. cereals, wheat, corn, rice, sphagnum, peat moss
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2307/02—Location of water treatment or water treatment device as part of a bottle
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    • C02F2307/04—Location of water treatment or water treatment device as part of a pitcher or jug
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    • C02F2307/06—Mounted on or being part of a faucet, shower handle or showerhead
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2307/00—Location of water treatment or water treatment device
    • C02F2307/10—Location of water treatment or water treatment device as part of a potable water dispenser, e.g. for use in homes or offices

Description

污染物質除去劑、碳/聚合物複合體、污染物質除去板片部件及濾材Contaminant remover, carbon/polymer composite, pollutant removal sheet member and filter material

本發明係關於一種污染物質除去劑、碳/聚合物複合體、污染物質除去板片部件及濾材。The present invention relates to a pollutant removing agent, a carbon/polymer composite, a pollutant removing sheet member, and a filter medium.

於用以淨化水之淨水器中，例如日本專利特開2001-205253、日本專利特開平06-106161中所揭示般多使用活性碳。又，淨水器例如多直接安裝於水管之水龍頭上而使用。In the water purifier for purifying water, activated carbon is often used as disclosed in Japanese Patent Laid-Open No. 2001-205253, and Japanese Patent Application Laid-Open No. Hei 06-106161. Moreover, the water purifier is used, for example, directly on a faucet of a water pipe.

[先前技術文獻][Previous Technical Literature] [專利文獻][Patent Literature]

[專利文獻1]日本專利特開2001-205253[Patent Document 1] Japanese Patent Laid-Open No. 2001-205253

[專利文獻2]日本專利特開平06-106161[Patent Document 2] Japanese Patent Laid-Open No. 06-106161

此種先前之淨水器存在以下問題：若過濾流量較多，即，若淨水器中流動之水之流速較快，則有時無法充分地發揮淨水功能。又，為增加比表面積，多使用活性碳之粉碎品，從而亦會產生經粉碎之活性碳與經淨化之水一起自淨水器漏出等問題。進而，對於可更有效地除去污染物質之污染物質除去劑、碳/聚合物複合體、污染物質除去板片部件有強烈之需求。又，亦期望藉由通過濾材而進行水之硬度之控制，但能夠達成上述期望之技術於本發明者所調查之範圍內並未為人所知。Such a previous water purifier has the following problem: if the filtration flow rate is large, that is, if the flow rate of the water flowing in the water purifier is fast, the water purification function may not be sufficiently exerted. Further, in order to increase the specific surface area, a pulverized product of activated carbon is often used, which also causes problems such as the pulverized activated carbon leaking from the water purifier together with the purified water. Further, there is a strong demand for a pollutant removing agent, a carbon/polymer composite, and a pollutant removing sheet member which can remove pollutants more effectively. Further, it is also desired to control the hardness of water by passing through the filter medium. However, the above-described desired technique is not known in the scope of investigation by the present inventors.

因此，本發明之第1目的在於提供一種可更有效地除去污染物質之污染物質除去劑、碳/聚合物複合體、污染物質除去板片部件、及濾材。又，本發明之第2目的在於提供一種即便過濾流量較多亦可充分地發揮淨化功能且不易產生與經淨化之流體一併流出等問題之濾材。進而，本發明之第3目的在於提供一種能夠進行水之硬度之控制之濾材。Accordingly, a first object of the present invention is to provide a pollutant removing agent, a carbon/polymer composite, a pollutant removing sheet member, and a filter material which can remove pollutants more effectively. Further, a second object of the present invention is to provide a filter material which can sufficiently exhibit a purifying function even when the filtration flow rate is large, and which is less likely to cause a flow out together with the purified fluid. Further, a third object of the present invention is to provide a filter material capable of controlling the hardness of water.

用以達成上述第1目的之本發明之第1態樣之污染物質除去劑包含如下多孔質碳材料：藉由氮BET(Brunauer-Emmett-Teller，布厄特)法所得之比表面積之值為1×102 m2 /克以上，藉由BJH(Barrett-Joyner-Halenda)法所得之孔隙之容積為0.3 cm3 /克以上、較佳為0.4 cm3 /克以上、更佳為0.5 cm3 /克以上，且粒徑為75 μm以上。再者，於方便上有時將此種多孔質碳材料稱為『本發明之第1態樣之多孔質碳材料』。此處，將粒徑未達75 μm之多孔質碳材料造粒所得之粒徑為75 μm以上之多孔質碳材料、或將粒徑未達75 μm之多孔質碳材料與粒徑為75 μm以上之多孔質碳材料混在之多孔質碳材料造粒所得之粒徑為75 μm以上之多孔質碳材料亦包含於本發明之「粒徑為75 μm以上之多孔質碳材料」中。於以下之說明中亦相同。The pollutant removing agent according to the first aspect of the present invention for achieving the above first object includes a porous carbon material having a specific surface area obtained by a nitrogen BET (Brunauer-Emmett-Teller) method. 1 × 10 2 m 2 /g or more, the volume of the pores obtained by the BJH (Barrett-Joyner-Halenda) method is 0.3 cm 3 /g or more, preferably 0.4 cm 3 /g or more, more preferably 0.5 cm 3 / gram or more, and the particle size is 75 μm or more. In addition, such a porous carbon material may be referred to as "the porous carbon material of the first aspect of the present invention" for convenience. Here, a porous carbon material having a particle diameter of 75 μm or more obtained by granulating a porous carbon material having a particle diameter of less than 75 μm or a porous carbon material having a particle diameter of less than 75 μm and a particle diameter of 75 μm The porous carbon material having a particle diameter of 75 μm or more obtained by granulating the porous carbon material in which the porous carbon material is mixed is also included in the "porous carbon material having a particle diameter of 75 μm or more" of the present invention. The same is true in the following description.

用以達成上述第1目的之本發明之第2態樣之污染物質除去劑包含如下多孔質碳材料：藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，藉由非定域化密度泛函數法求 出之直徑為1×10-9 m至5×10-7 m之孔隙之容積之合計為1.0 cm3 /克以上，且粒徑為75 μm以上。再者，於方便上有時將此種多孔質碳材料稱為『本發明之第2態樣之多孔質碳材料』。The pollutant removing agent according to the second aspect of the present invention for achieving the above first object includes a porous carbon material having a specific surface area obtained by a nitrogen BET method of 1 × 10 2 m 2 /g or more. The volume of the pores having a diameter of from 1 × 10 -9 m to 5 × 10 -7 m, which is obtained by the delocalized density-universal function method, is 1.0 cm 3 /g or more in total, and the particle diameter is 75 μm or more. Further, such a porous carbon material may be referred to as "the porous carbon material of the second aspect of the present invention" for convenience.

用以達成上述第1目的之本發明之第3態樣之污染物質除去劑包含如下多孔質碳材料：藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，於藉由非定域化密度泛函數法求出之孔隙徑分佈中在3 nm至20 nm之範圍內具有至少1個峰值，具有於3 nm至20 nm之範圍內之孔隙徑之孔隙之容積之合計所占之比率為所有孔隙之容積總計之0.2以上，且粒徑為75 μm以上。再者，於方便上有時將此種多孔質碳材料稱為『本發明之第3態樣之多孔質碳材料』。The pollutant removing agent according to the third aspect of the present invention for achieving the above first object includes a porous carbon material having a specific surface area obtained by a nitrogen BET method of 1 × 10 2 m 2 /g or more. The volume of the pore diameter distribution in the range of 3 nm to 20 nm in the pore diameter distribution obtained by the delocalized density function method, and the pore volume having a pore diameter in the range of 3 nm to 20 nm The total ratio is 0.2 or more of the total volume of all the pores, and the particle diameter is 75 μm or more. Further, such a porous carbon material may be referred to as "the porous carbon material of the third aspect of the present invention" for convenience.

用以達成上述第1目的之本發明之第4態樣之污染物質除去劑包含如下多孔質碳材料：藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，藉由汞滲法所得之孔隙之容積為1.0 cm3 /克以上，且粒徑為75 μm以上。再者，於方便上有時將此種多孔質碳材料稱為『本發明之第4態樣之多孔質碳材料』。The pollutant removing agent according to the fourth aspect of the present invention for achieving the above first object includes a porous carbon material having a specific surface area obtained by a nitrogen BET method of 1 × 10 2 m 2 /g or more. The volume of the pores obtained by the mercury infiltration method is 1.0 cm 3 /g or more, and the particle diameter is 75 μm or more. Further, such a porous carbon material may be referred to as "the porous carbon material of the fourth aspect of the present invention" for convenience.

用以達成上述第1目的之本發明之第1態樣之碳/聚合物複合體包含本發明之第1態樣之多孔質碳材料、及黏合劑。The carbon/polymer composite according to the first aspect of the present invention for achieving the above first object includes the porous carbon material according to the first aspect of the present invention and a binder.

用以達成上述第1目的之本發明之第2態樣之碳/聚合物複合體包含本發明之第2態樣之多孔質碳材料、及黏合劑。The carbon/polymer composite according to the second aspect of the present invention for achieving the above first object includes the porous carbon material of the second aspect of the present invention and a binder.

用以達成上述第1目的之本發明之第3態樣之碳/聚合物複合體包含本發明之第3態樣之多孔質碳材料、及黏合劑。The carbon/polymer composite according to the third aspect of the present invention for achieving the above first object includes the porous carbon material of the third aspect of the present invention and a binder.

用以達成上述第1目的之本發明之第4態樣之碳/聚合物複合體包含本發明之第4態樣之多孔質碳材料、及黏合劑。The carbon/polymer composite according to the fourth aspect of the present invention for achieving the above first object includes the porous carbon material of the fourth aspect of the present invention and a binder.

用以達成上述第1目的之本發明之第1態樣之污染物質除去板片部件包含本發明之第1態樣之多孔質碳材料、及支持部件。The pollutant removing sheet member according to the first aspect of the present invention for achieving the above first object includes the porous carbon material according to the first aspect of the present invention and a supporting member.

用以達成上述第1目的之本發明之第2態樣之污染物質除去板片部件包含本發明之第2態樣之多孔質碳材料、及支持部件。A pollutant removing sheet member according to a second aspect of the present invention for achieving the above first object includes the porous carbon material according to the second aspect of the present invention and a supporting member.

用以達成上述第1目的之本發明之第3態樣之污染物質除去板片部件包含本發明之第3態樣之多孔質碳材料、及支持部件。The pollutant removing sheet member according to the third aspect of the present invention for achieving the above first object includes the porous carbon material according to the third aspect of the present invention and a supporting member.

用以達成上述第1目的之本發明之第4態樣之污染物質除去板片部件包含本發明之第4態樣之多孔質碳材料、及支持部件。A contaminant removing sheet member according to a fourth aspect of the present invention for achieving the above first object includes the porous carbon material according to the fourth aspect of the present invention and a supporting member.

用以達成上述第2目的之本發明之第1態樣之濾材包含本發明之第1態樣之多孔質碳材料。The filter medium according to the first aspect of the present invention for achieving the above second object includes the porous carbon material according to the first aspect of the present invention.

用以達成上述第2目的之本發明之第2態樣之濾材包含本發明之第2態樣之多孔質碳材料。A filter material according to a second aspect of the present invention for achieving the above second object includes the porous carbon material of the second aspect of the present invention.

用以達成上述第2目的之本發明之第3態樣之濾材包含本發明之第3態樣之多孔質碳材料。The filter material according to the third aspect of the present invention for achieving the above second object includes the porous carbon material of the third aspect of the present invention.

用以達成上述第2目的之本發明之第4態樣之濾材包含本發明之第4態樣之多孔質碳材料。The filter material according to the fourth aspect of the present invention for achieving the above second object includes the porous carbon material of the fourth aspect of the present invention.

用以達成上述第3目的之本發明之第5態樣之濾材包含如下多孔質碳材料：藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，藉由BJH法所得之孔隙之容積為0.1 cm3 /克以上，且以含有選自由鈉、鎂、鉀及鈣所組成之群中之至少1種成分之植物為原料。The filter medium according to the fifth aspect of the present invention for achieving the above third object includes a porous carbon material having a specific surface area obtained by a nitrogen BET method of 1 × 10 2 m 2 /g or more by the BJH method. the resulting pore volume of less than 0.1 cm 3 / g, selected from the group consisting of and containing sodium, magnesium, potassium and calcium are composed of at least one plant component of the raw materials.

用以達成上述第3目的之本發明之第6態樣之濾材包含如下多孔質碳材料：藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，藉由非定域化密度泛函數法求出之直徑為1×10-9 m至5×10-7 m之孔隙之容積之合計為0.1 cm3 /克以上、較佳為0.2 cm3 /克以上，且以含有選自由鈉、鎂、鉀及鈣所組成之群中之至少1種成分之植物為原料。The filter material according to the sixth aspect of the present invention for achieving the above third object includes the following porous carbon material: the specific surface area obtained by the nitrogen BET method has a value of 1 × 10 2 m 2 /g or more, The volume of the pores having a diameter of from 1 × 10 -9 m to 5 × 10 -7 m, which is obtained by the domain density multivariate function method, is 0.1 cm 3 /g or more, preferably 0.2 cm 3 /g or more, and A plant containing at least one component selected from the group consisting of sodium, magnesium, potassium, and calcium is used as a raw material.

用以達成上述第3目的之本發明之第7態樣之濾材包含如下多孔質碳材料：藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，於藉由非定域化密度泛函數法求出之孔隙徑分佈中在3 nm至20 nm之範圍內具有至少1個峰值，具有於3 nm至20 nm之範圍內之孔隙徑之孔隙之容積之合計所占之比率為所有孔隙之容積總計之0.1以上，且以含有選自由鈉、鎂、鉀及鈣所組成之群中之至少1種成分之植物為原料。The filter material according to the seventh aspect of the present invention for achieving the above third object includes the following porous carbon material: the specific surface area obtained by the nitrogen BET method has a value of 1 × 10 2 m 2 /g or more, The total volume of the pores in the range of 3 nm to 20 nm in the pore diameter distribution obtained by the localized density-Fan-function method, and the volume of the pores having pore diameters in the range of 3 nm to 20 nm The ratio is 0.1 or more of the total volume of all the pores, and is made of a plant containing at least one component selected from the group consisting of sodium, magnesium, potassium, and calcium.

用以達成上述第3目的之本發明之第8態樣之濾材包含如下多孔質碳材料：藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，藉由汞滲法所得之孔隙之容積為1.0 cm3 /克以上，且以含有選自由鈉、鎂、鉀及鈣所組成之群中之至少1種成分之植物為原料。The filter medium according to the eighth aspect of the present invention for achieving the above third object comprises the following porous carbon material: a specific surface area obtained by a nitrogen BET method having a value of 1 × 10 2 m 2 /g or more, by mercury permeation The volume of the pores obtained by the method is 1.0 cm 3 /g or more, and is a plant containing at least one component selected from the group consisting of sodium, magnesium, potassium and calcium.

用以達成上述第1目的之本發明之第9態樣~第15態樣之濾材包含 本發明之第1態樣之多孔質碳材料，或包含本發明之第2態樣之多孔質碳材料，或包含本發明之第3態樣之多孔質碳材料，或包含本發明之第4態樣之多孔質碳材料。The ninth aspect to the fifteenth aspect of the present invention for achieving the above first object includes The porous carbon material according to the first aspect of the present invention, or the porous carbon material according to the second aspect of the present invention, or the porous carbon material according to the third aspect of the present invention, or the fourth aspect of the present invention A porous carbon material.

而且，本發明之第9態樣之濾材係於將含有分子量為1×102 至1×105 之物質1微克/升之水於空間速度為1200小時-1 下連續進行48小時通液時，直至該物質之除去率達到80%為止之時間為使用椰殼活性碳時之直至該物質之除去率達到80%為止之時間的2倍以上。此處，使用Kuraray Chemical股份有限公司製造之Kuraraycoal GW作為椰殼活性碳。Further, the ninth aspect of the present invention is characterized in that the water containing 1 μg/L of a substance having a molecular weight of 1 × 10 2 to 1 × 10 5 is continuously passed for 48 hours at a space velocity of 1200 hr -1 . The time until the removal rate of the substance reached 80% was twice or more the time until the removal rate of the substance reached 80% when the coconut shell activated carbon was used. Here, Kuraraycoal GW manufactured by Kuraray Chemical Co., Ltd. was used as coconut shell activated carbon.

又，本發明之第10態樣之濾材係於將含有0.9毫克/升十二烷基苯磺酸鹽之水於空間速度為1200小時-1 下連續進行25小時通液時，十二烷基苯磺酸鹽之除去率為10%以上。Further, the filter material according to the tenth aspect of the present invention is characterized in that the water containing 0.9 mg/liter of dodecylbenzenesulfonate is continuously passed through the liquid at a space velocity of 1200 hours -1 for 15 hours. The removal rate of the besylate salt is 10% or more.

又，本發明之第11態樣之濾材係於將含有6微克/升百菌清之水於空間速度為1200小時-1 下連續進行50小時通液時，百菌清之除去率為60%以上。Further, the filter material according to the eleventh aspect of the present invention is characterized in that the removal rate of chlorothalonil is 60% when the water containing 6 μg/L of chlorothalonil is continuously passed for 50 hours at a space velocity of 1200 hr -1 . the above.

又，本發明之第12態樣之濾材係於將含有6微克/升二氯松之水於空間速度為1200小時-1 下連續進行25小時通液時，二氯松之除去率為60%以上。Further, the filter material according to the twelfth aspect of the present invention is characterized in that the removal rate of diclosan is 60% when the water containing 6 μg/L of diclofen is continuously passed for 25 hours at a space velocity of 1200 hr -1 . the above.

又，本發明之第13態樣之濾材係於將含有6微克/升溶解性鉛之水於空間速度為1200小時-1 下連續進行25小時通液時，溶解性鉛之除去率為30%以上。Further, the filter material according to the thirteenth aspect of the present invention is characterized in that the removal rate of the soluble lead is 30% when the water containing 6 μg/liter of soluble lead is continuously passed for 25 hours at a space velocity of 1200 hours -1 . the above.

又，本發明之第14態樣之濾材係於將含有0.2毫克/升游離氯之水於空間速度為1200小時-1 下連續進行50小時通液時，游離氯之除去率為70%以上。Further, in the filter medium according to the fourteenth aspect of the present invention, when the water containing 0.2 mg/liter of free chlorine is continuously passed through the liquid at a space velocity of 1200 hr -1 for 50 hours, the removal rate of free chlorine is 70% or more.

又，本發明之第15態樣之濾材係於將含有以氯換算為130微克/升之總有機鹵素之水於空間速度1200小時-1 下連續進行5小時通液時，總有機鹵素之除去率為45%以上。Furthermore, if the first filter 15 aspect of the present invention based on the terms of chlorine containing 130 micrograms / liter of water of total organic halogen at a space velocity of 1200 hours -1 for 5 hours of continuous liquid flow, the total removal of organohalogen The rate is 45% or more.

於本發明之第1態樣~第4態樣之污染物質除去劑、本發明之第1態樣~第4態樣之碳/聚合物複合體、本發明之第1態樣~第4態樣之污染物質除去板片部件或本發明之第1態樣~第4態樣、第9態樣~第15態樣之濾材中，由於規定有所使用之多孔質碳材料之比表面積之值、各種孔隙之容積之值、孔隙分佈，故而可以較高之效率除去污染物質，可於較高之過濾流量下進行流體之淨化，且可以較高之效率除去所期望之物質。又，由於規定有多孔質碳材料之粒徑，故而不易產生多孔質碳材料伴與流體一併流出等問題。再者，本發明之第1態樣~第4態樣之污染物質除去劑、本發明之第1態樣~第4態樣之碳/聚合物複合體、本發明之第1態樣~第4態樣之污染物質除去板片部件或本發明之第1態樣~第4態樣之濾材係除吸附污染物質以外，例如亦基於HClO+C(多孔質碳材料)→CO(多孔質碳材料之表面)+H+ +Cl- 等化學反應而除去氯成分。又，於本發明之第5態樣~第8態樣之濾材中，由於規定有所使用之多孔質碳材料之比表面積之值、孔隙之容積之值、孔隙分佈，而且規定有原料，故而可進行通過濾材之水之硬度之控制。In the first aspect to the fourth aspect of the present invention, the pollutant removing agent, the first aspect to the fourth aspect of the present invention, the carbon/polymer composite, and the first aspect to the fourth aspect of the present invention The value of the specific surface area of the porous carbon material to be used is specified in the filter material of the first aspect to the fourth aspect, the ninth aspect to the fifteenth aspect of the present invention. The volume of various pores and the distribution of pores can remove pollutants at a higher efficiency, purify the fluid at a higher filtration flow rate, and remove the desired substance with higher efficiency. Further, since the particle diameter of the porous carbon material is specified, there is a problem that the porous carbon material does not easily flow out together with the fluid. Further, the first aspect to the fourth aspect of the present invention, the pollutant removing agent, the first aspect to the fourth aspect of the present invention, the carbon/polymer composite, and the first aspect of the present invention. The fourth aspect of the pollutant removing sheet member or the first aspect to the fourth aspect of the present invention is in addition to adsorbing pollutants, for example, based on HClO + C (porous carbon material) → CO (porous carbon) The surface of the material) is chemically reacted with +H + +Cl - to remove the chlorine component. Further, in the filter medium of the fifth aspect to the eighth aspect of the present invention, since the value of the specific surface area of the porous carbon material to be used, the value of the volume of the pores, the pore distribution, and the raw material are specified, The hardness of the water passing through the filter material can be controlled.

以下，參照圖式並基於實施例對本發明進行說明，但本發明並不限定於實施例，實施例中之各種數值或材料為例示。再者，說明係按照以下順序進行。Hereinafter, the present invention will be described with reference to the drawings, but the present invention is not limited to the examples, and various numerical values or materials in the examples are exemplified. Furthermore, the description is made in the following order.

1.與本發明之第1態樣~第4態樣之污染物質除去劑、本發明之第1態樣~第4態樣之碳/聚合物複合體、本發明之第1態樣~第4態樣之污染物質除去板片部件及本發明之第1態樣~第15態樣之濾材總體相關之說明1. A pollutant removing agent according to a first aspect to a fourth aspect of the present invention, a carbon/polymer composite according to a first aspect to a fourth aspect of the present invention, and a first aspect of the present invention. Description of the fourth embodiment of the pollutant-removing sheet member and the filter material of the first aspect to the fifteenth aspect of the present invention

2.實施例1(本發明之第1態樣~第4態樣之污染物質除去劑、本發明之第1態樣~第4態樣之碳/聚合物複合體、本發明之第1態樣~第4態樣之污染物質除去板片部件及本發明之第1態樣~第4態樣之濾材)2. Example 1 (Contaminant Removal Agent According to First Aspect to Fourth Aspect of the Present Invention, Carbon/Polymer Composite of First Aspect to Fourth Aspect of the Present Invention, and First Aspect of the Present Invention Sample to the fourth aspect of the pollutant removal sheet member and the first aspect of the present invention - the fourth aspect of the filter material)

3.實施例2(實施例1之變形)3. Embodiment 2 (Modification of Embodiment 1)

4.實施例3(實施例1之其他變形)4. Embodiment 3 (Other Modifications of Embodiment 1)

5.實施例4(實施例1之進而其他變形)5. Embodiment 4 (further variation of Embodiment 1)

6.實施例5(實施例1之進而其他變形)6. Embodiment 5 (further variation of Embodiment 1)

7.實施例6(本發明之第5態樣~第8態樣之濾材)7. Example 6 (the fifth aspect of the present invention ~ the eighth aspect of the filter material)

8.實施例7(本發明之第9態樣~第15態樣之濾材)8. Example 7 (the ninth aspect of the present invention ~ the filter material of the fifteenth aspect)

9.實施例8(實施例1~實施例7之變形)及其他9. Embodiment 8 (Modification of Embodiment 1 to Embodiment 7) and the like

[與本發明之第1態樣~第4態樣之污染物質除去劑、本發明 第1態樣~第4態樣之碳/聚合物複合體、本發明第1態樣~第4態樣之污染物質除去板片部件及本發明第1態樣~第15態樣之濾材總體相關之說明][Contrast material removing agent according to the first aspect to the fourth aspect of the present invention, the present invention The first aspect to the fourth aspect of the carbon/polymer composite, the first aspect to the fourth aspect of the present invention, the pollutant removing sheet member, and the filter material of the first aspect to the fifteenth aspect of the present invention Related instructions]

於以下說明中，有時將本發明之第1態樣~第4態樣之污染物質除去劑統一簡稱為『本發明之污染物質除去劑』，有時將本發明之第1態樣~第4態樣之碳/聚合物複合體統一簡稱為『本發明之碳/聚合物複合體』，有時將本發明之第1態樣~第4態樣之污染物質除去板片部件統一簡稱為『本發明之污染物質除去板片部件』，有時將本發明之第1態樣~第15態樣之濾材統一簡稱為『本發明之濾材』。又，有時將本發明之污染物質除去劑、本發明之碳/聚合物複合體、本發明之污染物質除去板片部件及本發明之濾材統一簡稱為『本發明』，有時將構成本發明之污染物質除去劑、本發明之碳/聚合物複合體、本發明之污染物質除去板片部件及本發明之第1態樣~第4態樣、第9態樣~第15態樣之濾材的多孔質碳材料統稱為『本發明之多孔質碳材料』。In the following description, the pollutant removing agent according to the first aspect to the fourth aspect of the present invention may be simply referred to as "the pollutant removing agent of the present invention", and the first aspect of the present invention may be used. The carbon/polymer composite of the fourth aspect is collectively referred to as "the carbon/polymer composite of the present invention", and the contaminant removing sheet member of the first aspect to the fourth aspect of the present invention may be simply referred to as In the "contaminant-removing sheet member of the present invention", the filter medium according to the first aspect to the fifteenth aspect of the present invention may be simply referred to as "the filter medium of the present invention". In addition, the contaminant removing agent of the present invention, the carbon/polymer composite of the present invention, the contaminant removing sheet member of the present invention, and the filter material of the present invention may be collectively referred to as "the present invention" in some cases. The pollutant removing agent of the invention, the carbon/polymer composite of the present invention, the pollutant removing sheet member of the present invention, and the first aspect to the fourth aspect, the ninth aspect to the fifteenth aspect of the present invention The porous carbon material of the filter medium is collectively referred to as "the porous carbon material of the present invention".

構成本發明之第1態樣之污染物質除去劑、本發明之第1態樣之碳/聚合物複合體、本發明之第1態樣之污染物質除去板片部件或本發明之第1態樣之濾材的多孔質碳材料並無限定，較佳為藉由汞滲法所得之孔隙之容積為1.5 cm3 /克以上。又，較佳為藉由MP(micropore，微孔)法所得之孔隙之容積為0.1 cm3 /克以上。The pollutant removing agent according to the first aspect of the present invention, the carbon/polymer composite according to the first aspect of the present invention, the pollutant removing sheet member according to the first aspect of the present invention, or the first aspect of the present invention The porous carbon material of the filter medium is not limited, and it is preferred that the volume of the pores obtained by the mercury infiltration method is 1.5 cm 3 /g or more. Further, it is preferable that the volume of the pores obtained by the MP (micropore) method is 0.1 cm 3 /g or more.

構成包括上述較佳形態之本發明之第1態樣~第4態樣之 污染物質除去劑或本發明之第1態樣~第4態樣、第9態樣~第15態樣之濾材的多孔質碳材料並無限定，較佳為多孔質碳材料之鬆密度為0.1克/cm3 至0.8克/cm3 。藉由將多孔質碳材料之鬆密度規定於上述範圍內，而無流體之流動受到多孔質碳材料阻礙之虞。即，可抑制因多孔質碳材料而導致之流體之壓力損失。The first embodiment to the fourth aspect of the present invention, including the first embodiment to the fourth aspect, the first aspect to the fourth aspect, and the ninth aspect to the fifteenth aspect of the filter material. The porous carbon material is not limited, and it is preferable that the bulk density of the porous carbon material is from 0.1 g/cm 3 to 0.8 g/cm 3 . By setting the bulk density of the porous carbon material within the above range, the flow of no fluid is hindered by the porous carbon material. That is, the pressure loss of the fluid due to the porous carbon material can be suppressed.

於包括以上說明之較佳形態之本發明之第5態樣~第8態樣之濾材中，多孔質碳材料如上述般以含有選自由鈉(Na)、鎂(Mg)、鉀(K)及鈣(Ca)所組成之群中之至少1種成分之植物為原料，藉由使用此種植物原料，於用作濾材之情形時，礦物成分較多地自多孔質碳材料溶出於過濾水中，其結果，可進行過濾水之硬度之控制。而且，於該情形時，可設為向硬度為0.1以下之水(試驗用水)50毫升中添加1克濾材，經過6小時後之硬度成為5以上之形態。再者，較佳為多孔質碳材料中包含以合計為0.4質量%以上之鈉(Na)、鎂(Mg)、鉀(K)及鈣(Ca)。此處，具體而言，作為植物原料，可列舉橘子皮、橙子皮、葡萄柚皮等柑橘類之皮、香蕉皮。In the filter medium of the fifth aspect to the eighth aspect of the present invention including the preferred embodiment described above, the porous carbon material contains, as described above, selected from the group consisting of sodium (Na), magnesium (Mg), and potassium (K). And a plant having at least one component selected from the group consisting of calcium (Ca), and by using the plant material, when used as a filter material, the mineral component is mostly dissolved from the porous carbon material in the filtered water. As a result, the hardness of the filtered water can be controlled. In this case, one gram of the filter medium may be added to 50 ml of water (test water) having a hardness of 0.1 or less, and the hardness after 5 hours may be 5 or more. In addition, it is preferable that the porous carbon material contains sodium (Na), magnesium (Mg), potassium (K), and calcium (Ca) in a total amount of 0.4% by mass or more. Here, specific examples of the plant material include citrus peels such as orange peel, orange peel, and grapefruit peel, and banana peel.

又，由上述構成本發明之第5態樣~第8態樣之濾材之多孔質碳材料，可構成包括作為以礦物補充為目的之礦物調整材料之功能性食品的各種功能性食品，包括作為以礦物補充為目的之礦物調整材料之化妝品的化妝品、化妝料等。再者，於功能性食品中，此外亦可包含例如賦形劑、黏合劑、崩解劑、潤滑劑、稀釋劑、調味劑、防腐劑、穩 定劑、著色劑、香料、維他命類、顯色劑、光澤劑、甜味劑、苦味劑、酸味劑、鮮味調味料、醱酵調味料、抗氧化劑、酵素、酵母萃取液、營養強化劑。作為功能性食品之形態，可列舉粉末狀、固體狀、錠劑狀、粒狀、顆粒狀、膠囊、乳脂狀、溶膠狀、凝膠狀、膠體狀。作為化妝品，例如可例示化妝水，化妝水含浸面膜，除去汗或油脂、口紅等污垢成分之潔面劑，作為化妝料中之其他成分，可列舉具有疏水性之美容成分之物質(例如大豆異黃酮、金雀異黃酮)，作為具有保濕效果及/或抗氧化效果之成分，可列舉玻尿酸、蝦紅素、維生素E、水溶性維生素E(Trolox)、輔酶Q10等化妝水中所含之有效成分。In addition, the porous carbon material constituting the filter medium of the fifth aspect to the eighth aspect of the present invention can constitute various functional foods including functional foods as mineral adjusting materials for mineral supplementation, including Cosmetics, cosmetics, etc. for cosmetics that are mineral-adjusted materials for mineral supplementation. Further, in the functional food, it may further contain, for example, an excipient, a binder, a disintegrant, a lubricant, a diluent, a flavoring agent, a preservative, and a stable Fixing agents, coloring agents, perfumes, vitamins, coloring agents, brighteners, sweeteners, bittering agents, sour agents, umami seasonings, yeast seasonings, antioxidants, enzymes, yeast extracts, nutritional supplements . Examples of the form of the functional food include a powder form, a solid form, a tablet form, a granule form, a granule form, a capsule form, a cream form, a sol form, a gel form, and a gel form. As a cosmetic, for example, a lotion such as a lotion, a lotion mask, and a moisturizing agent which removes a sweat component such as sweat, oil, or a lipstick, and the like, and other components in the cosmetic, a substance having a hydrophobic cosmetic component (for example, soy isoflavones) can be exemplified. And genistein, as a component having a moisturizing effect and/or an antioxidant effect, an active ingredient contained in a lotion such as hyaluronic acid, astaxanthin, vitamin E, water-soluble vitamin E (Trolox), and coenzyme Q10.

規定本發明之多孔質碳材料之粒徑為75 μm以上，該規定係基於JIS(Japanese Industrial Standards，日本工業標準)Z8801-1：2006「試驗用篩-第1部：金屬製網篩」。即，使用標稱網眼為75 μm之金屬網篩(所謂200網目之金屬網篩)進行試驗，規定為於未通過該金屬網篩之多孔質碳材料為90質量%以上時，粒徑為75 μm以上。又，於以下之說明中，將此種多孔質碳材料稱為「200網目未通過品」。將通過200網目之金屬網篩之多孔質碳材料稱為「200網目通過品」。於進行粒徑測定時，設為使用有本發明之多孔質碳材料之狀態，即，包括1次粒子、及複數之1次粒子集合而成之2次粒子之測定。The porous carbon material of the present invention has a particle diameter of 75 μm or more, and the regulation is based on JIS (Japanese Industrial Standards) Z8801-1:2006 "Test sieve - Part 1: Metal mesh screen". That is, the test is carried out using a metal mesh screen having a nominal mesh size of 75 μm (so-called 200 mesh metal mesh screen), and the particle size is defined as 90% by mass or more of the porous carbon material which does not pass through the metal mesh sieve. 75 μm or more. Moreover, in the following description, such a porous carbon material is referred to as "200 mesh unworked product". The porous carbon material passing through a 200 mesh metal mesh screen is referred to as "200 mesh passage product". In the measurement of the particle size, the state in which the porous carbon material of the present invention is used, that is, the measurement of the secondary particles including the primary particles and the plurality of primary particles is used.

又，藉由汞滲法所得之孔隙之測定係依據JIS R1655：2003「精密陶瓷之利用汞滲法之成形體氣孔徑分佈試驗方 法」。具體而言，使用汞孔隙計(PASCAL440：Thermo Electron公司製造)進行汞滲法測定。將孔隙測定區域設為15 μm~2 nm。Moreover, the measurement of the pores obtained by the mercury infiltration method is based on the test method for the pore size distribution of the shaped body by the mercury infiltration method of the precision ceramics according to JIS R1655:2003. law". Specifically, a mercury porosimetry measurement was performed using a mercury porosimeter (PASCAL 440: manufactured by Thermo Electron Co., Ltd.). The pore measurement area was set to 15 μm to 2 nm.

本發明之污染物質除去劑可用於例如水之淨化或空氣之淨化、廣而言之為流體之淨化。或者，本發明之污染物質除去劑可用作例如以除去有害物質或廢物為目的之除去劑。作為本發明之污染物質除去劑之使用形態，可例示以片狀之使用、填充於管柱或濾筒中之狀態下之使用、收納於具有透水性之袋中之狀態下之使用、使用黏合劑(黏結劑)等賦形為所期望之形狀之狀態下之使用、以粉狀之使用。於用作分散於溶液中之污染物質除去劑之情形時，可對表面進行親水處理或疏水處理而使用。由本發明之碳/聚合物複合體或污染物質除去板片部件可構成例如空氣淨化裝置之過濾器、口罩、防護手套或防護靴。The pollutant removing agent of the present invention can be used, for example, for purification of water or purification of air, and in general, for purification of fluids. Alternatively, the pollutant removing agent of the present invention can be used as, for example, a removing agent for the purpose of removing harmful substances or waste. The use form of the pollutant removing agent of the present invention is exemplified by use in a sheet form, use in a state of being filled in a column or a filter cartridge, use in a state in which a bag having water permeability is contained, and use of a binder. (Adhesive agent) or the like is used in a state in which it is shaped into a desired shape, and is used in powder form. In the case of being used as a pollutant removing agent dispersed in a solution, the surface may be subjected to a hydrophilic treatment or a hydrophobic treatment. The sheet member removed from the carbon/polymer composite or contaminant of the present invention may constitute, for example, a filter, a mask, a protective glove or a protective boot of an air purifying device.

於包括以上較佳形態之本發明之污染物質除去板片部件中，作為支持部件，可列舉織布或不織布，作為構成支持部件之材料，可列舉纖維素或聚丙烯、聚酯。而且，作為污染物質除去板片部件之形態，可列舉本發明之多孔質碳材料夾持於支持部件與支持部件之間之形態、多孔質碳材料捏合於支持部件中之形態。或者，作為污染物質除去板片部件之形態，可列舉本發明之碳/聚合物複合體夾持於支持部件與支持部件之間之形態、本發明之碳/聚合物複合體捏合於支持部件中之形態。作為構成碳/聚合物複合體之黏合劑，例如可列舉羧基硝化纖維素。In the contaminant removing sheet member of the present invention including the above preferred embodiment, a woven fabric or a non-woven fabric is exemplified as the supporting member, and examples of the material constituting the supporting member include cellulose, polypropylene, and polyester. In addition, the form in which the porous carbon material of the present invention is sandwiched between the support member and the support member and the porous carbon material is kneaded in the support member is exemplified. Alternatively, as a form of the pollutant removing sheet member, the carbon/polymer composite of the present invention may be sandwiched between the supporting member and the supporting member, and the carbon/polymer composite of the present invention may be kneaded in the supporting member. The form. Examples of the binder constituting the carbon/polymer composite include a carboxylated nitrocellulose.

適合裝入包括上述較佳形態之本發明之濾材的淨化裝置、具體而言為淨水器(以下有時稱為「本發明之淨水器」)可設為進而具有過濾膜(例如開有0.4 μm~0.01 μm之孔之中空纖維膜或平板膜)之構成(本發明之濾材與過濾膜之併用)，可設為進而具有逆浸透膜(RO，Reverse Osmosis)之構成(本發明之濾材與逆浸透膜之併用)，可設為進而具有陶瓷製之濾材(具有微細之孔之陶瓷製之濾材)之構成(本發明之濾材與陶瓷製之濾材之併用)，亦可設為進而具有離子交換樹脂之構成(本發明之濾材與離子交換樹脂之併用)。再者，一般而言，通過逆浸透膜(RO)之過濾水中幾乎不含礦物成分，藉由使過濾水於通過逆浸透膜(RO)後通過本發明之濾材，可含有礦物成分。A purifying apparatus, particularly a water purifier (hereinafter sometimes referred to as "the purifier of the present invention"), which is suitable for the filter medium of the present invention, which is preferably in the above-described preferred embodiment, may further comprise a filter membrane (for example, The configuration of the hollow fiber membrane or the flat membrane of the pores of 0.4 μm to 0.01 μm (the filter medium of the present invention and the filtration membrane) may be further configured to have a reverse osmosis (RO) (the filter medium of the present invention) In combination with a reverse osmosis membrane, it may be configured to have a ceramic filter material (a filter material made of ceramic having fine pores) (the filter medium of the present invention may be used in combination with a filter material made of ceramics), or may further have The composition of the ion exchange resin (the filter medium of the present invention is used in combination with an ion exchange resin). Further, in general, the filtered water passing through the reverse osmosis membrane (RO) contains almost no mineral component, and the filtered water can pass through the reverse osmosis membrane (RO) and pass through the filter medium of the present invention to contain a mineral component.

作為本發明之淨水器之種類，可列舉連續式淨水器、批次式淨水器、逆浸透膜淨水器，或者，可列舉於水管之水龍頭之前端部直接安裝淨水器本體之水龍頭直連型、固定型(亦稱為廚上型或桌上型)、於水栓中裝入有淨水器之水栓一體化型、設置於廚房之水槽內之廚下型(內置型)、於水瓶或水壺等容器內裝入有淨水器之水瓶型(水罐型)、直接安裝於水管計量儀之後的水管配管上之中央型、可攜型、吸管型。本發明之淨水器之構成、構造可設為與先前之淨水器相同之構成、構造。於本發明之淨水器中，本發明之濾材(多孔質碳材料)例如可收納於濾筒中而使用，只要於濾筒設置水流入部及水排出部即可。於本發明之淨水器中應成為淨化對象之「水」並不限定於JIS S3201：2010 「家庭用淨水器試驗方法」之「3.用語及定義」中所規定之「水」。Examples of the type of the water purifier of the present invention include a continuous type water purifier, a batch type water purifier, and a reverse osmosis membrane water purifier, or a direct installation of a water purifier body at a front end of a water pipe faucet. Direct faucet type, fixed type (also known as kitchen type or table type), hydrant integrated type with water purifier installed in the water hydrant, and kitchen type set in the kitchen sink (built-in type) In a container such as a water bottle or a kettle, a water bottle type (water tank type) equipped with a water purifier, and a central type, a portable type, and a suction tube type which are directly attached to a water pipe of the water pipe meter. The structure and structure of the water purifier of the present invention can be set to the same configuration and structure as the prior water purifier. In the water purifier of the present invention, the filter medium (porous carbon material) of the present invention can be used, for example, in a filter cartridge, and the water inflow portion and the water discharge portion may be provided in the filter cartridge. The "water" to be purified in the water purifier of the present invention is not limited to JIS S3201:2010 "Water" as defined in "3. Terms and Definitions" of the "Test Method for Household Water Purifiers".

或者，作為適合裝入本發明之濾材之部件，可列舉帶帽或蓋、帶吸管部件、帶噴霧部件之瓶(所謂寶特瓶)或層壓容器、塑膠容器、玻璃容器、玻璃瓶等之帽或蓋。此處，於帽或蓋之內部配置本發明之濾材，使瓶或層壓容器、塑膠容器、玻璃容器、玻璃瓶等內之液體或水(飲用水或化妝水等)通過配置於帽或蓋之內部之本發明之濾材而飲用或使用，藉此可使過濾水中含有礦物成分。或者，亦可採用如下形態：於具有透水性之袋中儲存本發明之濾材，將該袋投入至瓶(所謂寶特瓶)或層壓容器、塑膠容器、玻璃容器、玻璃瓶、水瓶等各種容器內之液體或水(飲用水或化妝水等)中。Alternatively, as a member suitable for the filter medium of the present invention, a cap or a cap, a pipette member, a bottle with a spray member (a so-called PET bottle) or a laminated container, a plastic container, a glass container, a glass bottle, etc. may be mentioned. Cap or cover. Here, the filter medium of the present invention is disposed inside the cap or the lid, and the liquid or water (drinking water or lotion, etc.) in the bottle or the laminated container, the plastic container, the glass container, the glass bottle, or the like is disposed in the cap or the lid. The filter medium of the present invention is used for drinking or use, whereby the filtered water contains mineral components. Alternatively, the filter medium of the present invention may be stored in a bag having water permeability, and the bag may be put into a bottle (so-called bottle) or a laminated container, a plastic container, a glass container, a glass bottle, a water bottle, or the like. Liquid or water in the container (drinking water or lotion, etc.).

於將本發明之多孔質碳材料之原料設為含有矽(Si)之源自植物之材料之情形時，具體而言，雖並不限定於此，但較理想為多孔質碳材料中之灼燒餘物(殘留灰分)之含有率為15質量%以下。又，較理想為以下敍述之多孔質碳材料前驅物或碳質物質中之灼燒餘物(殘留灰分)之含有率為20質量%以上。此處，灼燒餘物(殘留灰分)係指將於120℃下乾燥12小時所得之試樣於空氣(乾燥空氣)中加熱至800℃時所殘留之物質之質量%，具體而言，可基於熱重量測定法(TG，Thermogravimetry)法進行測定。When the raw material of the porous carbon material of the present invention is a plant-derived material containing cerium (Si), specifically, it is not limited thereto, but it is preferably a burning in a porous carbon material. The content of the burned matter (residual ash) is 15% by mass or less. Moreover, it is preferable that the content of the burning residue (residual ash) in the porous carbon material precursor or the carbonaceous material described below is 20% by mass or more. Here, the burning residue (residual ash) refers to the mass % of the substance remaining when the sample obtained by drying at 120 ° C for 12 hours is heated to 800 ° C in air (dry air), specifically, The measurement was carried out based on a thermogravimetry (TG) method.

本發明之多孔質碳材料、或構成本發明之第5態樣~第8態樣之濾材之多孔質碳材料例如可藉由將源自植物之材料 於400℃至1400℃下碳化後以酸或鹼進行處理而獲得。於此種多孔質碳材料之製造方法(以下有時簡稱為『多孔質碳材料之製造方法』)中，將藉由使源自植物之材料於400℃至1400℃下碳化而得之材料且以酸或鹼進行處理前之材料稱為『多孔質碳材料前驅物』或『碳質物質』。The porous carbon material of the present invention or the porous carbon material constituting the filter medium of the fifth aspect to the eighth aspect of the present invention can be, for example, a plant-derived material. It is obtained by treatment with an acid or a base after carbonization at 400 ° C to 1400 ° C. In the method for producing such a porous carbon material (hereinafter sometimes simply referred to as "the method for producing a porous carbon material"), a material obtained by carbonizing a plant-derived material at 400 ° C to 1400 ° C and The material before treatment with acid or alkali is called "porous carbon material precursor" or "carbonaceous material".

多孔質碳材料之製造方法中，可於以酸或鹼進行處理後包括實施活化處理之步驟，亦可於實施活化處理後以酸或鹼進行處理。又，於包括此種較佳形態之多孔質碳材料之製造方法中，雖亦取決於所使用之源自植物之材料，但亦可於將源自植物之材料碳化前，在較用於碳化之溫度低之溫度(例如400℃~700℃)下以阻斷氧之狀態對源自植物之材料實施加熱處理(預碳化處理)。藉此，可萃取於碳化過程中可能生成之焦油成分，其結果，可減少或除去於碳化過程中可能生成之焦油成分。再者，阻斷氧之狀態例如可藉由設為氮氣或氬氣等惰性氣體環境、或藉由設為真空環境、或藉由使源自植物之材料成為一種蒸烤狀態而達成。又，於多孔質碳材料之製造方法中，雖亦取決於所使用之源自植物之材料，但有時為使源自植物之材料中所含之礦物成分或水分減少，又，為防止碳化過程中之異臭之產生，可使源自植物之材料浸漬於酸或鹼中，亦可浸漬於醇(例如甲醇或乙醇、異丙醇)中。再者，於多孔質碳材料之製造方法中，亦可於上述步驟後執行預碳化處理。作為以於惰性氣體中實施加熱處理為宜之材料，例如可列舉較多地產生木醋(焦油或輕質油分)之植物。又，作為以實施利 用醇之前處理為宜之材料，例如可列舉較多地含有碘或各種礦物之海藻類。In the method for producing a porous carbon material, the step of performing the activation treatment may be carried out after treatment with an acid or a base, or may be treated with an acid or a base after the activation treatment. Further, in the method for producing a porous carbon material including such a preferred embodiment, it depends on the plant-derived material used, but it can also be used for carbonization before carbonizing the plant-derived material. The plant-derived material is subjected to heat treatment (pre-carbonization treatment) at a temperature lower than the temperature (for example, 400 ° C to 700 ° C) in a state of blocking oxygen. Thereby, the tar component which may be generated during the carbonization process can be extracted, and as a result, the tar component which may be generated during the carbonization process can be reduced or removed. Further, the state of blocking oxygen can be achieved, for example, by using an inert gas atmosphere such as nitrogen or argon, or by setting it as a vacuum environment, or by making the plant-derived material into a steamed state. Further, in the method for producing a porous carbon material, depending on the plant-derived material to be used, the mineral component or water contained in the plant-derived material may be reduced to prevent carbonization. The odor generated in the process may be such that the plant-derived material is immersed in an acid or a base, or may be immersed in an alcohol (for example, methanol or ethanol, isopropyl alcohol). Further, in the method for producing a porous carbon material, the pre-carbonization treatment may be performed after the above steps. As a material suitable for heat treatment in an inert gas, for example, a plant which produces a large amount of wood vinegar (tar or light oil) can be mentioned. Also, as an implementation A suitable material for the treatment with an alcohol is, for example, seaweed which contains a large amount of iodine or various minerals.

多孔質碳材料之製造方法係將源自植物之材料於400℃至1400℃下碳化，此處，所謂碳化一般係指對有機物質(於本發明之多孔質碳材料、或構成本發明之第5態樣~第8態樣之濾材之多孔質碳材料之情形時為源自植物之材料)進行熱處理而使其轉換為碳質物質(例如參照JIS M0104-1984)。再者，作為用於碳化之環境，可列舉阻斷氧之環境，具體而言，可列舉真空環境、氮氣或氬氣等惰性氣體環境、使源自植物之材料成為一種蒸烤狀態之環境。作為直至碳化溫度為止之升溫速度，雖並無限定，但於該環境下可列舉1℃/分鐘以上，較佳為3℃/分鐘以上，更佳為5℃/分鐘以上。又，作為碳化時間之上限，可列舉10小時，較佳為7小時，更佳為5小時，但並不限定於此。碳化時間之下限只要設為可確實將源自植物之材料碳化之時間即可。又，可將源自植物之材料根據需要粉碎而成為所期望之粒度，亦可進行分級。亦可預先清洗源自植物之材料。或者，可將所獲得之多孔質碳材料前驅物或多孔質碳材料按照需要粉碎而成為所期望之粒度，亦可進行分級。或者，可將活化處理後之多孔質碳材料按照需要粉碎而成為所期望之粒度，亦可進行分級。進而，亦可對最終所得之多孔質碳材料實施殺菌處理。用於碳化之爐之形式、構成、構造並無限制，可設為連續爐，亦可設為批次爐(batch爐)。The method for producing a porous carbon material is to carbonize a plant-derived material at 400 ° C to 1400 ° C. Here, the term "carbonization" generally means a pair of organic substances (the porous carbon material of the present invention or the first aspect of the present invention) In the case of the porous carbon material of the filter material of the eighth aspect to the eighth aspect, the material derived from the plant is subjected to heat treatment to be converted into a carbonaceous substance (for example, refer to JIS M0104-1984). Further, examples of the environment for carbonization include an environment in which oxygen is blocked, and specifically, an inert gas atmosphere such as a vacuum atmosphere, nitrogen gas or argon gas, or an environment in which a plant-derived material is in a steamed state. The rate of temperature rise up to the carbonization temperature is not limited, but in this environment, it is 1 ° C / min or more, preferably 3 ° C / min or more, and more preferably 5 ° C / min or more. Further, the upper limit of the carbonization time is 10 hours, preferably 7 hours, more preferably 5 hours, but is not limited thereto. The lower limit of the carbonization time may be set to a time at which the material derived from the plant can be surely carbonized. Further, the plant-derived material may be pulverized as needed to have a desired particle size, or may be classified. Plant-derived materials can also be pre-cleaned. Alternatively, the obtained porous carbon material precursor or porous carbon material may be pulverized as needed to have a desired particle size, or may be classified. Alternatively, the activated carbon material after the activation treatment may be pulverized as needed to have a desired particle size, or may be classified. Further, the porous carbon material finally obtained can be sterilized. The form, structure, and structure of the furnace for carbonization are not limited, and may be a continuous furnace or a batch furnace.

於多孔質碳材料之製造方法中，若如上述般實施活化處 理，則可使孔徑小於2 nm之微孔隙(於下文敍述)增加。作為活化處理之方法，可列舉氣體活化法、化學品活化法。此處，所謂氣體活化法係如下之方法：使用氧或水蒸氣、二氧化碳、空氣等作為活化劑，於該氣體環境下且於700℃至1400℃下、較佳為於700℃至1000℃下、更佳為於800℃至950℃下將多孔質碳材料加熱數十分鐘至數小時，藉此利用多孔質碳材料中之揮發成分或碳分子使微細構造擴展。再者，更具體而言，加熱溫度基於源自植物之材料之種類、氣體之種類或濃度等進行適當選擇即可。所謂化學品活化法係指使用氯化鋅、氯化鐵、磷酸鈣、氫氧化鈣、碳酸鎂、碳酸鉀、硫酸等代替氣體活化法中使用之氧或水蒸氣進行活化，以鹽酸進行清洗，以鹼性水溶液調整pH值，且進行乾燥之方法。In the method for producing a porous carbon material, if the activation is carried out as described above The microporosity (described below) with a pore size of less than 2 nm can be increased. Examples of the method of the activation treatment include a gas activation method and a chemical activation method. Here, the gas activation method is a method in which oxygen or water vapor, carbon dioxide, air or the like is used as an activator, and in the gas atmosphere, at 700 ° C to 1400 ° C, preferably at 700 ° C to 1000 ° C More preferably, the porous carbon material is heated at 800 ° C to 950 ° C for several tens of minutes to several hours, whereby the fine structure is expanded by the volatile component or carbon molecule in the porous carbon material. Furthermore, more specifically, the heating temperature may be appropriately selected depending on the type of the plant-derived material, the type or concentration of the gas, and the like. The chemical activation method refers to the use of zinc chloride, ferric chloride, calcium phosphate, calcium hydroxide, magnesium carbonate, potassium carbonate, sulfuric acid, etc. instead of the oxygen or water vapor used in the gas activation method for activation, and washing with hydrochloric acid. The pH is adjusted with an aqueous alkaline solution and dried.

亦可對本發明之多孔質碳材料之表面、或構成本發明之第5態樣~第8態樣之濾材之多孔質碳材料之表面進行化學處理或分子改質。作為化學處理，例如可列舉藉由硝酸處理而於表面生成羧基之處理。又，亦可藉由進行與利用水蒸氣、氧、鹼等之活化處理相同之處理，而於多孔質碳材料之表面生成羥基、羧基、酮基、酯基等各種官能基。進而，亦可藉由與可與多孔質碳材料反應之具有羥基、羧基、胺基等之化學種或蛋白質進行化學反應而進行分子改質。The surface of the porous carbon material of the present invention or the surface of the porous carbon material constituting the filter medium of the fifth aspect to the eighth aspect of the present invention may be chemically treated or molecularly modified. As the chemical treatment, for example, a treatment of forming a carboxyl group on the surface by a nitric acid treatment can be mentioned. Further, various functional groups such as a hydroxyl group, a carboxyl group, a ketone group, and an ester group may be formed on the surface of the porous carbon material by performing the same treatment as the activation treatment using steam, oxygen, or alkali. Further, molecular modification may be carried out by chemical reaction with a chemical species or protein having a hydroxyl group, a carboxyl group, an amine group or the like which can react with the porous carbon material.

於多孔質碳材料之製造方法中，藉由利用酸或鹼之處理而除去碳化後之源自植物之材料中之矽成分。此處，作為 矽成分，可列舉二氧化矽或氧化矽、氧化矽鹽等矽氧化物。如上所述，藉由除去碳化後之源自植物之材料中之矽成分，可獲得具有較高之比表面積之多孔質碳材料。有時亦可基於乾式蝕刻法而除去碳化後之源自植物之材料中之矽成分。又，例如可藉由浸漬於鹽酸、硝酸、硫酸等無機酸中而除去碳化後之源自植物之材料中所含之礦物成分。In the method for producing a porous carbon material, the ruthenium component in the carbonized plant-derived material is removed by treatment with an acid or a base. Here, as Examples of the cerium component include cerium oxide, cerium oxide, and cerium oxide. As described above, by removing the ruthenium component in the carbon-derived plant-derived material, a porous carbon material having a high specific surface area can be obtained. It is also possible to remove the ruthenium component in the carbonized plant-derived material based on the dry etching method. Further, for example, the mineral component contained in the carbonized plant-derived material can be removed by immersing in a mineral acid such as hydrochloric acid, nitric acid or sulfuric acid.

本發明之多孔質碳材料可將源自植物之材料設為原料。此處，作為源自植物之材料，可列舉米(稻)、大麥、小麥、黑麥、稗(稗)、粟(粟)等之稻殼或稻桿、珈琲豆、茶葉(例如綠茶或紅茶等之葉)、甘蔗類(更具體而言為甘蔗類之殘渣)、玉米類(更具體而言為玉米類之芯)、上述果實之皮(例如橘子等柑橘類之皮或香蕉皮等)、或蘆葦、裙帶菜梗絲，但並不限定於該等，此外亦可列舉例如植生於陸地上之維管束植物、蕨類植物、苔蘚植物、藻類、海草。再者，可將該等材料單獨用作原料，亦可混合複數種而使用。又，源自植物之材料之形狀或形態亦無特別限定，例如可為稻殼或稻桿本身，或亦可為乾燥處理品。進而，於啤酒或洋酒等飲食品加工中，亦可使用實施有醱酵處理、烘培處理、萃取處理等各種處理者。尤其，就謀求產業廢棄物之資源化之觀點而言，較佳為使用脫粒等加工後之稻桿或稻殼。該等加工後之稻桿或稻殼例如可自農業協同組合或酒類製造公司、食品公司、食品加工公司大量且容易地獲得。The porous carbon material of the present invention can use a plant-derived material as a raw material. Here, examples of the plant-derived material include rice husk or rice straw, cowpea, and tea (such as green tea or black tea) such as rice (rice), barley, wheat, rye, medlar, and millet. Leaves, etc., sugar cane (more specifically, sugarcane residue), corn (more specifically, corn core), skin of the above fruit (such as citrus peel or banana peel, such as orange), Or reeds, wakame stems, but not limited to these, in addition to vascular plants, ferns, bryophytes, algae, seaweed, for example, planted on land. Further, these materials may be used alone as a raw material, or may be used in combination of plural kinds. Further, the shape or form of the material derived from the plant is not particularly limited, and may be, for example, rice husk or rice straw itself, or may be a dried product. Further, in the processing of foods and drinks such as beer or wine, various processors such as fermentation treatment, baking treatment, and extraction treatment may be used. In particular, from the viewpoint of resource utilization of industrial waste, it is preferred to use rice straw or rice husk after processing such as threshing. Such processed rice straws or rice husks can be obtained, for example, in large quantities and easily from agricultural synergistic combinations or liquor manufacturing companies, food companies, food processing companies.

本發明之多孔質碳材料中亦可含有鎂(Mg)、鉀(K)、鈣 (Ca)、或磷(P)、硫(S)等非金屬元素、過渡元素等金屬元素。作為鎂(Mg)之含有率，可列舉0.01質量%以上3質量%以下，作為鉀(K)之含有率，可列舉0.01質量%以上3質量%以下，作為鈣(Ca)之含有率，可列舉0.05質量%以上3質量%以下，作為磷(P)之含有率，可列舉0.01質量%以上3質量%以下，作為硫(S)之含有率，可列舉0.01質量%以上3質量%以下。再者，就比表面積之值增加等觀點而言，以該等元素之含有率較少為宜。多孔質碳材料中亦可含有除上述元素以外之元素，當然上述各種元素之含有率之範圍亦可變更。The porous carbon material of the present invention may also contain magnesium (Mg), potassium (K), and calcium. (Ca), or a metal element such as a non-metallic element such as phosphorus (P) or sulfur (S) or a transition element. The content of magnesium (Mg) may be, for example, 0.01% by mass or more and 3% by mass or less, and the content of potassium (K) may be, for example, 0.01% by mass or more and 3% by mass or less, and the content of calcium (Ca) may be The content of phosphorus (P) is, for example, 0.01% by mass or more and 3% by mass or less, and the content of sulfur (S) is 0.01% by mass or more and 3% by mass or less. Further, from the viewpoints of an increase in the value of the specific surface area, it is preferred that the content of the elements be small. The porous carbon material may contain elements other than the above elements, and the range of the content ratio of the above various elements may be changed.

對於本發明之多孔質碳材料、或構成本發明之第5態樣~第8態樣之濾材之多孔質碳材料，可使用例如能量分散型X射線分析裝置(例如日本電子股份有限公司製造之JED-2200F)藉由能量分散法(EDS，Energy Dispersive Spectroscopy)進行各種元素之分析。此處，將測定條件設為例如掃描電壓15 kV、照射電流10 μA即可。For the porous carbon material of the present invention or the porous carbon material constituting the filter medium according to the fifth aspect to the eighth aspect of the present invention, for example, an energy dispersive X-ray analyzer (for example, manufactured by JEOL Ltd.) can be used. JED-2200F) Analysis of various elements by Energy Dispersive Spectroscopy (EDS). Here, the measurement conditions may be, for example, a scanning voltage of 15 kV and an irradiation current of 10 μA.

本發明之多孔質碳材料、或構成本發明之第5態樣~第8態樣之濾材之多孔質碳材料具有較多之孔隙(pore)。孔隙包括孔徑為2 nm至50 nm之『中孔隙』、孔徑小於2 nm之『微孔隙』、及孔徑超過50 nm之『大孔隙』。又，於本發明之多孔質碳材料中，藉由MP法所得之孔隙之容積如上述般較佳為0.1 cm3 /克以上。The porous carbon material of the present invention or the porous carbon material constituting the filter medium of the fifth aspect to the eighth aspect of the present invention has a large number of pores. The pores include "middle pores" with a pore size of 2 nm to 50 nm, "micropores" with a pore diameter of less than 2 nm, and "macropores" with a pore diameter of more than 50 nm. Further, in the porous carbon material of the present invention, the volume of the pores obtained by the MP method is preferably 0.1 cm 3 /g or more as described above.

於本發明之多孔質碳材料、或構成本發明之第5態樣~第8態樣之濾材之多孔質碳材料中，為獲得更優異之功能 性，較理想為藉由氮BET法所得之比表面積之值(以下有時簡稱為『比表面積之值』)較佳為4×102 m2 /克以上。In the porous carbon material of the present invention or the porous carbon material constituting the filter medium according to the fifth aspect to the eighth aspect of the present invention, in order to obtain more excellent functionality, it is preferably obtained by the nitrogen BET method. The value of the specific surface area (hereinafter sometimes simply referred to as "the value of the specific surface area") is preferably 4 × 10 2 m 2 /g or more.

所謂氮BET法係指藉由使吸附劑(此處為多孔質碳材料)吸附或脫附作為吸附分子之氮而測定吸附等溫線，且基於以式(1)表示之BET式分析所測定之資料之方法，可基於該方法算出比表面積或孔隙容積等。具體而言，於藉由氮BET法算出比表面積之值之情形時，首先藉由使多孔質碳材料吸附或脫附作為吸附分子之氮，而求出吸附等溫線。繼而，根據所獲得之吸附等溫線，基於式(1)或將式(1)變形所得之式(1')而算出[p/{Va (p0 -p)}]，對平衡相對壓力(p/p0 )進行繪圖。繼而，將該曲線視為直線，基於最小平方法算出斜率s(=[(C-1)/(C．Vm )])及截距i(=[1/(C．Vm )])。繼而，根據所求出之斜率s及截距i，基於式(2-1)、式(2-2)算出Vm 及C。進而，根據Vm ，基於式(3)算出比表面積asBET (參照日本bel股份有限公司製造之BELSORP-mini及BELSORP分析軟體之說明書，第62頁~第66頁)。再者，該氮BET法係依據JIS R1626-1996「精密陶瓷粉體之利用氣體吸附BET法之比表面積之測定方法」之測定方法。The nitrogen BET method is an adsorption isotherm measured by adsorbing or desorbing an adsorbent (here, a porous carbon material) as nitrogen of an adsorption molecule, and is determined based on a BET-type analysis represented by the formula (1). The method of the data can calculate the specific surface area, the pore volume, and the like based on the method. Specifically, when the value of the specific surface area is calculated by the nitrogen BET method, the adsorption isotherm is first obtained by adsorbing or desorbing the porous carbon material as nitrogen of the adsorption molecule. Then, based on the obtained adsorption isotherm, [p/{V a (p 0 -p)}] is calculated based on the formula (1) or the formula (1') obtained by deforming the formula (1), and the equilibrium is relatively The pressure (p/p 0 ) is plotted. Then, the curve is regarded as a straight line, and the slope s (=[(C-1)/(C.V m )))) and the intercept i(=[1/(C.V m )]) are calculated based on the least squares method. . Then, based on the obtained slope s and the intercept i, V m and C are calculated based on the equations (2-1) and (2-2). Further, based on V m , the specific surface area a sBET is calculated based on the formula (3) (refer to the specification of the BELSORP -mini and BELSORP analysis software manufactured by Nippon Steel Co., Ltd., page 62 to page 66). Further, the nitrogen BET method is based on the measurement method of JIS R1626-1996 "Method for Measuring Specific Surface Area by Gas Adsorption BET Method of Precision Ceramic Powder".

Va =(Vm ．C．p)/[(p0 -p){1+(C-1)(p/p0 )}] (1)V a =(V m .C.p)/[(p 0 -p){1+(C-1)(p/p 0 )}] (1)

[p/{Va (p0 -p)}]=[(C-1)/(C．Vm )](p/p0 )+[1/(C．Vm )] (1')[p/{V a (p 0 -p)}]=[(C-1)/(C.V m )](p/p 0 )+[1/(C.V m )] (1')

Vm =1/(s+i) (2-1)V m =1/(s+i) (2-1)

C=(s/i)+1 (2-2)C=(s/i)+1 (2-2)

asBET =(Vm ．L．σ)/22414 (3)a sBET =(V m .L.σ)/22414 (3)

其中， Va ：吸附量Where V a : adsorption amount

Vm ：單分子層之吸附量V m : adsorption amount of monolayer

p：氮之平衡時之壓力p: pressure at the balance of nitrogen

p0 ：氮之飽和蒸氣壓p 0 : saturated vapor pressure of nitrogen

L：亞佛加厥數(Avogadro number)L: Avogadro number

σ：氮之吸附剖面積。σ: area of adsorption of nitrogen.

於藉由氮BET法算出孔隙容積Vp 之情形時，例如對所求出之吸附等溫線之吸附資料進行線性內插，求出於孔隙容積算出相對壓力下設定之相對壓力下之吸附量V。可根據該吸附量V，基於式(4)算出孔隙容積Vp (參照日本bel股份有限公司製造之BELSORP-mini及BELSORP分析軟體之說明書，第62頁~第65頁)。再者，以下有時將基於氮BET法之孔隙容積簡稱為『孔隙容積』。When the pore volume V p is calculated by the nitrogen BET method, for example, the adsorption data of the obtained adsorption isotherm are linearly interpolated, and the adsorption amount at the relative pressure set under the relative pressure of the pore volume is calculated. V. The pore volume V p can be calculated based on the adsorption amount V based on the formula (4) (refer to the specification of the BELSORP-mini and BELSORP analysis software manufactured by Japan bel Co., Ltd., page 62 to page 65). Further, in the following, the pore volume based on the nitrogen BET method may be simply referred to as "pore volume".

Vp =(V/22414)×(Mg /ρg ) (4)V p =(V/22414)×(M g /ρ g ) (4)

其中，V：相對壓力下之吸附量Where V: the amount of adsorption under relative pressure

Mg ：氮之分子量M g : molecular weight of nitrogen

ρg ：氮之密度。ρ g : density of nitrogen.

中孔隙之孔徑例如可基於BJH法由相對於該孔徑之孔隙容積變化率而作為孔隙之分佈算出。BJH法為被廣泛用作孔隙分佈分析法之方法。於基於BJH法進行孔隙分佈分析之情形時，首先藉由使多孔質碳材料吸附或脫附作為吸附分子之氮，而求出脫附等溫線。繼而，基於所求出之脫附等溫線，求出自孔隙由吸附分子(例如氮)填滿之狀態起吸 附分子階段性地吸脫時之吸附層之厚度、及此時產生之孔之內徑(芯半徑之2倍)，基於式(5)算出孔隙半徑rp ，基於式(6)算出孔隙容積。繼而，根據孔隙半徑及孔隙容積將相對於孔隙徑(2rp )之孔隙容積變化率(dVp /drp )繪圖，藉此獲得孔隙分佈曲線(參照日本bel股份有限公司製造之BELSORP-mini及BELSORP分析軟體之說明書，第85頁~第88頁)。The pore diameter of the mesopores can be calculated, for example, from the distribution of pores by the BJH method from the rate of change in pore volume with respect to the pore diameter. The BJH method is widely used as a method of pore distribution analysis. In the case of performing pore distribution analysis based on the BJH method, first, a desorption isotherm is obtained by adsorbing or desorbing a porous carbon material as nitrogen of an adsorption molecule. Then, based on the obtained desorption isotherm, the thickness of the adsorption layer when the adsorption molecules are gradually absorbed from the state in which the pores are filled by the adsorption molecules (for example, nitrogen), and the pores generated at this time are determined. The inner diameter (twice the core radius), the pore radius r p was calculated based on the formula (5), and the pore volume was calculated based on the formula (6). Then, according to the pore radius and the pore volume relative to pore diameter (2r p) a rate of change of pore volume (dV p / dr p) drawing, thereby obtaining the pore distribution curve (refer to Japanese bel manufacturing Co. of BELSORP-mini and BELSORP Analysis Software Manual, pages 85 to 88).

rp =t+rk (5)r p =t+r k (5)

Vpn =Rn ．dVn -Rn ．dtn ．c．ΣApj (6)V pn =R n . dV n -R n . Dt n . c. ΣA pj (6)

其中， Rn =rpn 2 /(rkn -1+dtn )2 (7)Where R n =r pn 2 /(r kn -1+dt n ) 2 (7)

此處，rp ：孔隙半徑Here, r p : pore radius

rk ：於該壓力下厚度為t之吸附層吸附於孔隙半徑為rp 之孔隙之內壁之情形時的芯半徑(內徑/2)r k : core radius (inner diameter / 2) when the adsorption layer having a thickness t of the pressure is adsorbed on the inner wall of the pore having a pore radius of r p under the pressure

Vpn ：氮之第n次之吸脫產生時之孔隙容積V pn : the pore volume at the time of the nth suction of nitrogen

dVn ：此時之變化量dV n : the amount of change at this time

dtn ：氮之第n次之吸脫產生時之吸附層之厚度tn 之變化量Dt n : the amount of change in the thickness t n of the adsorption layer at the time of the nth absorption of nitrogen

rkn ：此時之芯半徑r kn : core radius at this time

c：固定值c: fixed value

rpn ：氮之第n次之吸脫產生時之孔隙半徑r pn : pore radius at the time of the nth absorption of nitrogen

又，ΣApj 表示j=1至j=n-1之孔隙之壁面之面積之累計值。Further, ΣA pj represents the cumulative value of the area of the wall surface of the pores of j=1 to j=n-1.

微孔隙之孔徑例如可基於MP法由相對於該孔徑之孔隙容積變化率而作為孔隙之分佈算出。於藉由MP法進行孔隙分佈分析之情形時，首先藉由使多孔質碳材料吸附氮， 而求出吸附等溫線。繼而，將該吸附等溫線轉換為相對於吸附層之厚度t之孔隙容積(對t進行繪圖)。繼而，可基於該曲線之曲率(相對於吸附層之厚度t之變化量的孔隙容積之變化量)而獲得孔隙分佈曲線(參照日本bel股份有限公司製造之BELSORP-mini及BELSORP分析軟體之說明書，第72頁~第73頁、第82頁)。The pore diameter of the micropore can be calculated, for example, based on the MP method from the pore volume change rate with respect to the pore diameter as the pore distribution. In the case of pore distribution analysis by the MP method, first, by adsorbing nitrogen to the porous carbon material, The adsorption isotherm is determined. The adsorption isotherm is then converted to a pore volume (plotted with respect to t) relative to the thickness t of the adsorbent layer. Then, the pore distribution curve can be obtained based on the curvature of the curve (the amount of change in the pore volume with respect to the change in the thickness t of the adsorption layer) (refer to the specification of the BELSORP-mini and BELSORP analysis software manufactured by Japan bel Co., Ltd., Page 72 ~ page 73, page 82).

於JIS Z8831-2：2010「粉體(固體)之孔隙徑分佈及孔隙特性-第2部：利用氣體吸附之中孔隙及大孔隙之測定方法」、及JIS Z8831-3：2010「粉體(固體)之孔隙徑分佈及孔隙特性-第3部：利用氣體吸附之微孔隙之測定方法」中規定之非定域化密度泛函數法(NLDFT法，Non Localized Density Functional Theory法)中，使用附屬於日本bel股份有限公司製造之自動比表面積/孔隙分佈測定裝置「BELSORP-MAX」之軟體作為分析軟體。作為前提條件，將模型設為圓筒形狀，假設為碳黑(CB，Carbon Black)，且將孔隙分佈參數之分佈函數設為「no-assumption(無假設)」，而對所獲得之分佈資料實施10次平滑化。JIS Z8831-2:2010 "Pore diameter distribution and pore characteristics of powder (solid) - Part 2: Determination of pores and macropores by gas adsorption", and JIS Z8831-3: 2010 "Powder ( The pore diameter distribution and pore characteristics of the solids - Part 3: Non-localized Density Functional Theory (NLDFT method) specified in the method for measuring micropores by gas adsorption The soft body attached to the automatic specific surface area/pore distribution measuring device "BELSORP-MAX" manufactured by Japan bel Co., Ltd. is used as an analysis software. As a precondition, the model is set to a cylindrical shape, assuming carbon black (CB, Carbon Black), and the distribution function of the pore distribution parameter is set to "no-assumption", and the obtained distribution data is obtained. Perform 10 smoothings.

以酸或鹼處理多孔質碳材料前驅物，作為具體之處理方法，例如可列舉將多孔質碳材料前驅物浸漬於酸或鹼之水溶液中之方法、或使多孔質碳材料前驅物與酸或鹼於氣相下反應之方法。更具體而言，於藉由酸進行處理之情形時，作為酸，例如可列舉氟化氫、氫氟酸、氟化銨、氟化鈣、氟化鈉等顯示酸性之氟化合物。於使用氟化合物之情 形時，氟元素相對於多孔質碳材料前驅物中所含之矽成分中之矽元素成為4倍之量即可，較佳為氟化合物水溶液之濃度為10質量%以上。於藉由氫氟酸除去多孔質碳材料前驅物中所含之矽成分(例如二氧化矽)之情形時，二氧化矽如化學式(A)或化學式(B)所示般與氫氟酸反應，而作為六氟矽酸(H2 SiF6 )或四氟化矽(SiF4 )被除去，從而可獲得多孔質碳材料。繼而，其後進行清洗、乾燥即可。於藉由酸進行處理之情形時，例如可藉由以鹽酸、硝酸、硫酸等無機酸進行處理而除去多孔質碳材料前驅物中所含之礦物成分。The porous carbon material precursor is treated with an acid or a base, and as a specific treatment method, for example, a method of immersing a porous carbon material precursor in an aqueous solution of an acid or a base, or a porous carbon material precursor with an acid or A method in which a base is reacted in the gas phase. More specifically, when it is treated with an acid, examples of the acid include fluorine compounds which exhibit acidity such as hydrogen fluoride, hydrofluoric acid, ammonium fluoride, calcium fluoride, and sodium fluoride. In the case of using a fluorine compound, the fluorine element may be added in an amount of four times the amount of the lanthanum element in the cerium component contained in the porous carbon material precursor, and the concentration of the fluorine compound aqueous solution is preferably 10% by mass or more. In the case where the ruthenium component (for example, ruthenium dioxide) contained in the precursor of the porous carbon material is removed by hydrofluoric acid, the ruthenium dioxide is reacted with hydrofluoric acid as shown in the chemical formula (A) or the chemical formula (B). Further, as a hexafluoroantimonic acid (H 2 SiF 6 ) or cesium tetrafluoride (SiF 4 ), a porous carbon material can be obtained. Then, it can be washed and dried. In the case of treatment with an acid, for example, the mineral component contained in the precursor of the porous carbon material can be removed by treatment with a mineral acid such as hydrochloric acid, nitric acid or sulfuric acid.

SiO2 +6HF → H2 SiF6 +2H2 O (A)SiO 2 +6HF → H 2 SiF 6 +2H 2 O (A)

SiO2 +4HF → SiF4 +2H2 O (B)SiO 2 +4HF → SiF 4 +2H 2 O (B)

又，於藉由鹼(鹼基)進行處理之情形時，作為鹼，例如可列舉氫氧化鈉。於使用鹼之水溶液之情形時，水溶液之pH值為11以上即可。於藉由氫氧化鈉水溶液除去多孔質碳材料前驅物中所含之矽成分(例如二氧化矽)之情形時，藉由加熱氫氧化鈉水溶液，使二氧化矽如化學式(C)所示般發生反應，而作為矽酸鈉(Na2 SiO3 )被除去，從而可獲得多孔質碳材料。又，於使氫氧化鈉於氣相下發生反應而進行處理之情形時，藉由加熱氫氧化鈉之固體，如化學式(C)所示般進行反應，而作為矽酸鈉(Na2 SiO3 )被除去，從而可獲得多孔質碳材料。繼而，其後進行清洗、乾燥即可。Further, in the case of treatment with a base (base), examples of the base include sodium hydroxide. In the case of using an aqueous solution of an alkali, the pH of the aqueous solution may be 11 or more. When the bismuth component (for example, cerium oxide) contained in the precursor of the porous carbon material is removed by the aqueous solution of sodium hydroxide, the cerium oxide is heated as shown in the chemical formula (C) by heating the aqueous sodium hydroxide solution. The reaction takes place and is removed as sodium citrate (Na 2 SiO 3 ), whereby a porous carbon material can be obtained. Further, in the case where sodium hydroxide is reacted in the gas phase for treatment, a solid of sodium hydroxide is heated to carry out a reaction as shown in the chemical formula (C), and as sodium citrate (Na 2 SiO 3 ) ) is removed to obtain a porous carbon material. Then, it can be washed and dried.

SiO2 +2NaOH → Na2 SiO3 +H2 O (C)SiO 2 +2NaOH → Na 2 SiO 3 +H 2 O (C)

或者，作為本發明之多孔質碳材料、或構成本發明之第 5態樣~第8態樣之濾材之多孔質碳材料，例如亦可使用日本專利特開2010-106007中揭示之空孔具有3維規則性之多孔質碳材料(所謂的具有反蛋白石構造之多孔質碳材料)，具體而言為具備具有1×10-9 m至1×10-5 m之平均直徑的3維排列之球狀空孔、且表面積為3×102 m2 /克以上之多孔質碳材料，較佳為於宏觀上以相當於結晶構造之狀態排列有空孔、或於宏觀上以相當於面心立方結構之(111)面配向之配置狀態於表面排列有空孔之多孔質碳材料。Alternatively, as the porous carbon material of the present invention or the porous carbon material constituting the filter medium of the fifth aspect to the eighth aspect of the present invention, for example, the pores disclosed in Japanese Patent Laid-Open Publication No. 2010-106007 may be used. A three-dimensional regular porous carbon material (so-called porous carbon material having an inverse opal structure), specifically, a three-dimensional array having an average diameter of from 1 × 10 -9 m to 1 × 10 -5 m The porous carbon material having a spherical pore size and a surface area of 3 × 10 2 m 2 /g or more is preferably macroscopically arranged with pores in a state corresponding to a crystal structure or macroscopically equivalent to a face center. The (111) plane alignment of the cubic structure is in a porous carbon material in which pores are arranged on the surface.

[實施例1][Example 1]

實施例1係關於本發明之第1態樣~第4態樣之污染物質除去劑、本發明之第1態樣~第4態樣之碳/聚合物複合體、本發明之第1態樣~第4態樣之污染物質除去板片部件及本發明之第1態樣~第4態樣之濾材。Example 1 relates to a pollutant removing agent according to a first aspect to a fourth aspect of the present invention, a carbon/polymer composite according to a first aspect to a fourth aspect of the present invention, and a first aspect of the present invention. ~ The fourth aspect of the pollutant removing sheet member and the filter material of the first aspect to the fourth aspect of the present invention.

關於實施例1之污染物質除去劑或濾材，若按照本發明之第1態樣之污染物質除去劑或濾材予以表達，則包含如下多孔質碳材料：藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，藉由BJH法所得之孔隙之容積為0.3 cm3 /克以上、較佳為0.4 cm3 /克以上、更佳為0.5 cm3 /克以上，且粒徑為75 μm以上。又，若按照本發明之第2態樣之污染物質除去劑或濾材予以表達，則包含如下多孔質碳材料：藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，藉由非定域化密度泛函數法(NLDFT法，Non Localized Density Functional Theory法)求出之直徑為1×10-9 m至5×10-7 m之孔隙之容積之合計(於方便上稱為『容積 A』)為1.0 cm3 /克以上，且粒徑為75 μm以上。進而，若按照本發明之第3態樣之污染物質除去劑或濾材予以表達，則包含如下多孔質碳材料：藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，於藉由非定域化密度泛函數法求出之孔隙徑分佈中在3 nm至20 nm之範圍內具有至少1個峰值，具有於3 nm至20 nm之範圍內之孔隙徑之孔隙之容積之合計所占之比率為所有孔隙之容積總計之0.2以上，且粒徑為75 μm以上。又，若按照本發明之第4態樣之污染物質除去劑或濾材予以表達，則包含如下多孔質碳材料：藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，藉由汞滲法所得之孔隙之容積為1.0 cm3 /克以上，且粒徑為75 μm以上。When the pollutant removing agent or the filter medium of the first embodiment is expressed by the pollutant removing agent or the filter medium according to the first aspect of the present invention, the porous carbon material is contained as follows: the specific surface area value obtained by the nitrogen BET method The volume of the pores obtained by the BJH method is 0.3 cm 3 /g or more, preferably 0.4 cm 3 /g or more, more preferably 0.5 cm 3 /g or more, and is 1 × 10 2 m 2 /g or more. The diameter is 75 μm or more. Further, when the pollutant removing agent or the filter medium according to the second aspect of the present invention is expressed, the porous carbon material is obtained by a value of a specific surface area obtained by a nitrogen BET method of 1 × 10 2 m 2 /g or more. The total volume of the pores having a diameter of 1 × 10 -9 m to 5 × 10 -7 m is determined by the non-localized density functional method (NLDFT method, Non Localized Density Functional Theory method) The above is referred to as "volume A") and is 1.0 cm 3 /g or more, and the particle diameter is 75 μm or more. Further, when the pollutant removing agent or the filter medium according to the third aspect of the present invention is expressed, the porous carbon material is obtained by a value of a specific surface area obtained by a nitrogen BET method of 1 × 10 2 m 2 /g or more. a pore diameter distribution in the range of 3 nm to 20 nm in the pore diameter distribution obtained by the delocalized density functional method, and a pore diameter in the range of 3 nm to 20 nm The ratio of the total volume is 0.2 or more of the total volume of all the pores, and the particle diameter is 75 μm or more. Further, when the pollutant removing agent or the filter medium according to the fourth aspect of the present invention is expressed, the porous carbon material is contained: the specific surface area obtained by the nitrogen BET method is 1 × 10 2 m 2 /g or more. The volume of the pores obtained by the mercury infiltration method is 1.0 cm 3 /g or more, and the particle diameter is 75 μm or more.

再者，利用BJH法之孔隙(中孔隙)、利用MP法之孔隙(微孔隙)、及利用汞滲法之孔隙係藉由自至少含有矽之源自植物之材料中除去矽而獲得。更佳為多孔質碳材料之藉由汞滲法所得之孔隙之容積為2.0 cm3 /克以上，藉由MP法所得之孔隙之容積較佳為0.1 cm3 /克以上。又，多孔質碳材料之鬆密度較佳為0.1克/cm3 至0.8克/cm3 。Further, the pores (middle pores) by the BJH method, the pores (micropores) by the MP method, and the pores by the mercury infiltration method are obtained by removing ruthenium from a plant-derived material containing at least ruthenium. More preferably, the volume of the pores obtained by the mercury infiltration method for the porous carbon material is 2.0 cm 3 /g or more, and the volume of the pores obtained by the MP method is preferably 0.1 cm 3 /g or more. Further, the bulk density of the porous carbon material is preferably from 0.1 g/cm 3 to 0.8 g/cm 3 .

於實施例1中，將多孔質碳材料之原料即源自植物之材料設為米(稻)之稻殼。而且，實施例1中之多孔質碳材料係藉由將作為原料之稻殼碳化使其轉換為碳質物質(多孔質碳材料前驅物)，其次實施酸處理而獲得。以下，對實施例1中之多孔質碳材料之製造方法進行說明。In Example 1, the raw material of the porous carbon material, that is, the plant-derived material, was set as the rice husk of rice (rice). Further, the porous carbon material in the first embodiment is obtained by carbonizing a rice hull as a raw material to be converted into a carbonaceous material (porous carbon material precursor), and secondarily performing an acid treatment. Hereinafter, a method for producing the porous carbon material in Example 1 will be described.

於實施例1中之多孔質碳材料之製造中，藉由將源自植 物之材料於400℃至1400℃下碳化後以酸或鹼進行處理而獲得多孔質碳材料。即，首先於惰性氣體中對稻殼實施加熱處理(預碳化處理)。具體而言，藉由將稻殼於氮氣流中以500℃加熱5小時而使其碳化，從而獲得碳化物。再者，可藉由進行此種處理，而減少或除去後續之碳化時可能生成之焦油成分。其後，將10克該碳化物加入至氧化鋁製之坩堝中，於氮氣流中(10升/分鐘)以5℃/分鐘之升溫速度使其升溫至800℃。繼而，於800℃下碳化1小時使其轉換為碳質物質(多孔質碳材料前驅物)後冷卻至室溫。再者，於碳化及冷卻中使氮氣持續流通。其次，藉由使該多孔質碳材料前驅物於46容積%之氫氟酸水溶液中浸漬一晚而進行酸處理後，使用水及乙醇清洗至pH值成為7為止。其次，於120℃下進行乾燥後，藉由於900℃下且於水蒸氣氣流中(5升/分鐘)中加熱3小時而進行活化處理，藉此可獲得實施例1之多孔質碳材料。繼而，粉碎實施例1之多孔質碳材料並進行篩選，選取60網目通過、200網目未通過之部分，而獲得實施例1A。In the manufacture of the porous carbon material in Embodiment 1, by originating from the plant The material of the material is carbonized at 400 ° C to 1400 ° C and then treated with an acid or a base to obtain a porous carbon material. That is, the rice husk is first subjected to heat treatment (pre-carbonization treatment) in an inert gas. Specifically, the rice hull was carbonized by heating at 500 ° C for 5 hours in a nitrogen stream to obtain a carbide. Further, by performing such a treatment, the tar component which may be generated upon subsequent carbonization can be reduced or removed. Thereafter, 10 g of this carbide was placed in a crucible made of alumina, and the temperature was raised to 800 ° C in a nitrogen stream (10 liter / min) at a temperature elevation rate of 5 ° C / min. Then, it was carbonized at 800 ° C for 1 hour to be converted into a carbonaceous substance (porous carbon material precursor), and then cooled to room temperature. Further, nitrogen gas is continuously circulated during carbonization and cooling. Next, the porous carbon material precursor was immersed in a 46% by volume aqueous solution of hydrofluoric acid for one night to carry out an acid treatment, and then washed with water and ethanol until the pH became 7. Next, after drying at 120 ° C, the activation treatment was carried out by heating at 900 ° C for 3 hours in a steam gas stream (5 liter / minute), whereby the porous carbon material of Example 1 was obtained. Then, the porous carbon material of Example 1 was pulverized and subjected to screening, and a portion of 60 mesh passage and 200 mesh unpassed was selected to obtain Example 1A.

藉由篩選市售之淨水器中使用之濾材，而選取60網目通過、200網目未通過之部分，將其設為比較例1A及比較例1B。再者，比較例1A中之濾材包含二氧化矽，比較例1B中之濾材包含竹碳。By screening the filter materials used in the commercially available water purifier, 60 mesh passages and 200 mesh unpassed portions were selected and compared as Comparative Example 1A and Comparative Example 1B. Further, the filter medium in Comparative Example 1A contains cerium oxide, and the filter medium in Comparative Example 1B contains bamboo carbon.

使用BELSORP-mini(日本bel股份有限公司製造)作為用以求出比表面積及孔隙容積之測定機器，進行氮吸附脫附試驗。作為測定條件，將測定平衡相對壓力(p/p0 )設為 0.01~0.99。繼而，基於BELSORP分析軟體算出比表面積及孔隙容積。又，中孔隙及微孔隙之孔隙徑分佈係進行使用有上述測定機器之氮吸附脫附試驗，藉由BELSORP分析軟體且基於BJH法及MP法而算出。進而，於基於非定域化密度泛函數法(NLDFT法)之測定中使用日本bel股份有限公司製造之自動比表面積/孔隙分佈測定裝置「BELSORP-MAX」。再者，於進行測定時，作為試樣之前處理，於200℃下進行3小時之乾燥。A BELSORP-mini (manufactured by Nippon Steel Co., Ltd.) was used as a measuring device for obtaining a specific surface area and a pore volume, and a nitrogen adsorption desorption test was performed. As the measurement conditions, the measured equilibrium relative pressure (p/p 0 ) was set to 0.01 to 0.99. Then, the specific surface area and pore volume were calculated based on the BELSORP analysis software. Further, the pore diameter distribution of the mesopores and the micropores was measured by a nitrogen adsorption desorption test using the above-described measuring apparatus, and analyzed by the BELSORP analysis software based on the BJH method and the MP method. Further, an automatic specific surface area/pore distribution measuring apparatus "BELSORP-MAX" manufactured by Nippon Steel Co., Ltd. was used for the measurement based on the delocalized density functional method (NLDFT method). Further, in the measurement, the sample was pretreated as a sample, and dried at 200 ° C for 3 hours.

對實施例1A、比較例1A及比較例1B之濾材測定比表面積及孔隙容積，結果獲得表1所示之結果。再者，於表1中，「比表面積」係指藉由氮BET法所得之比表面積之值，單位為m2 /克。又，「MP法」、「BJH法」表示藉由MP法所得之孔隙(微孔隙)之容積測定結果、藉由BJH法所得之孔隙(中孔隙~大孔隙)之容積測定結果，單位為cm3 /克。又，於表1中，「所有孔隙容積」係指藉由氮BET法所得之所有孔隙容積之值，單位為cm3 /克。進而，將基於非定域化密度泛函數法(NLDFT法)的具有於3 nm至20 nm之範圍內之孔隙徑之孔隙之容積之合計相對於直徑為1×10-9 m至5×10-7 m之孔隙之容積之合計(容積A，所有孔隙之容積總計)所占的比率(容積比率)示於表2。再者，比較例1A中之基於BJH法之孔隙容積測定結果、及基於NLDFT法之所有孔隙之容積總計(容積A)測定結果表示為較大之值，其原因在於比較例1A中之濾材包含二氧化矽，而並非包含多孔質碳材料。The specific surface area and pore volume of the filter materials of Example 1A, Comparative Example 1A and Comparative Example 1B were measured, and the results shown in Table 1 were obtained. Further, in Table 1, "specific surface area" means the value of the specific surface area obtained by the nitrogen BET method, and the unit is m 2 /g. In addition, the "MP method" and the "BJH method" indicate the volume measurement results of the pores (microporoses) obtained by the MP method, and the volume measurement results of the pores (middle pores to large pores) obtained by the BJH method, and the unit is cm. 3 / gram. Further, in Table 1, "all pore volumes" means the values of all pore volumes obtained by the nitrogen BET method in units of cm 3 /g. Further, the total volume of the pores having the pore diameters in the range of 3 nm to 20 nm based on the delocalized density functional method (NLDFT method) is 1 × 10 -9 m to 5 × in diameter. The ratio (volume ratio) of the total volume of the pores of 10 -7 m (volume A, total volume of all pores) is shown in Table 2. Further, the results of the pore volume measurement based on the BJH method in Comparative Example 1A and the volume total (volume A) measurement results of all the pores based on the NLDFT method are shown as large values because the filter medium in Comparative Example 1A contains Ceria is not a porous carbon material.

為進行吸附量測定，製備0.03莫耳/升之亞甲基藍及0.5毫莫耳/升之黑5之水溶液，且對各40毫升之水溶液投入10毫克試樣。繼而，使用旋轉混合器(攪拌機)以100 rpm進行攪拌，將攪拌時間設為0.5分鐘、1分鐘、3分鐘、5分鐘、15分鐘、30分鐘、60分鐘、180分鐘進行攪拌後進行過濾，基於測定所獲得之濾液之吸光度變化之試驗法，根據由每單位質量之吸光度獲得之校準曲線之值算出攪拌時間與毎1克濾材之亞甲基藍及黑5之吸附量之關係。For the measurement of the adsorption amount, an aqueous solution of 0.03 mol/L of methylene blue and 0.5 mmol/L of black 5 was prepared, and a 10 mg sample was placed for each 40 ml of the aqueous solution. Then, the mixture was stirred at 100 rpm using a rotary mixer (mixer), and the mixture was stirred for 0.5 minutes, 1 minute, 3 minutes, 5 minutes, 15 minutes, 30 minutes, 60 minutes, and 180 minutes, and then filtered. The test method for measuring the change in absorbance of the obtained filtrate was carried out, and the relationship between the stirring time and the adsorption amount of methylene blue and black 5 of 1 g of the filter material was calculated from the value of the calibration curve obtained from the absorbance per unit mass.

將其結果示於圖1(A)及(B)，實施例1A之濾材之亞甲基藍及黑5之吸附量明顯大於比較例1A及比較例1B之濾材之吸附量，認為其係比較例中未觀察到之大容積之中孔隙及大孔隙之影響。再者，圖1之縱軸為吸附量(單位：毫克/克)，橫軸為試驗時間(將濾材浸漬於試驗液中之時間，單位為分鐘)。又，三角符號表示實施例1A之資料，方形符號表示比較例1A之資料，圓形符號表示比較例1B之資料。The results are shown in Fig. 1 (A) and (B). The adsorption amount of methylene blue and black 5 of the filter material of Example 1A is significantly larger than that of the filter materials of Comparative Example 1A and Comparative Example 1B, and it is considered that it is not in the comparative example. The effects of pores and macropores in the large volume were observed. Further, the vertical axis of Fig. 1 is the adsorption amount (unit: mg/g), and the horizontal axis is the test time (the time in which the filter medium is immersed in the test liquid, the unit is minute). Further, the triangular symbol indicates the data of the embodiment 1A, the square symbol indicates the data of the comparative example 1A, and the circular symbol indicates the data of the comparative example 1B.

又，使用乳缽以人工將其他製造批次中之實施例1之濾材粉碎，設為實施例1B之濾材，實施例1B之濾材為200網目未通過品，粒徑為0.50 mm至0.85 mm。又，將同時獲得之200網目通過品之濾材設為參考例1。測定比表面積及孔隙容積，結果獲得表1所示之結果。進而，自市售之淨水器中取出活性碳，自該等活性碳中選取粒徑為0.50 mm至0.85 mm者，並作為比較例1C及比較例1D進行評估。Further, the filter medium of Example 1 in another batch was manually pulverized using a mortar, and the filter material of Example 1B was used. The filter material of Example 1B was a 200 mesh unpeeled product having a particle diameter of 0.50 mm to 0.85 mm. Further, the filter medium of the 200 mesh passage product obtained at the same time was referred to as Reference Example 1. The specific surface area and pore volume were measured, and as a result, the results shown in Table 1 were obtained. Further, activated carbon was taken out from a commercially available water purifier, and those having a particle diameter of 0.50 mm to 0.85 mm were selected from the activated carbons, and evaluated as Comparative Example 1C and Comparative Example 1D.

進而，將200毫克之實施例1B、參考例1、比較例1C及 比較例1D之試樣分別填充於濾筒中，使亞甲基藍水溶液以50毫升/分鐘之流速流入濾筒中，測定自濾筒流出之水之亞甲基藍濃度。將其結果示於圖2。再者，圖2之縱軸為亞甲基藍吸附率(除去率)，且為將參考例1之濾材之吸附量(除去率)設為100%而標準化之值。又，橫軸為亞甲基藍水溶液之流量。根據圖2亦判斷出實施例1B(以方形符號表示)、參考例1(以菱形符號表示)之濾材之亞甲基藍吸附量明顯高於比較例1C(以三角符號表示)或比較例1D(以圓形符號表示)。Further, 200 mg of Example 1B, Reference Example 1, Comparative Example 1C and The samples of Comparative Example 1D were each filled in a filter cartridge, and an aqueous solution of methylene blue was flowed into the filter cartridge at a flow rate of 50 ml/min, and the concentration of methylene blue in the water flowing out from the cartridge was measured. The results are shown in Fig. 2. In addition, the vertical axis of FIG. 2 is a methylene blue adsorption ratio (removal rate), and is a value normalized by setting the adsorption amount (removal rate) of the filter medium of Reference Example 1 to 100%. Further, the horizontal axis is the flow rate of the methylene blue aqueous solution. It is also judged from Fig. 2 that the methylene blue adsorption amount of the filter material of Example 1B (indicated by a square symbol) and Reference Example 1 (indicated by a diamond symbol) is significantly higher than that of Comparative Example 1C (indicated by a triangular symbol) or Comparative Example 1D (in a circle) The shape symbol indicates).

將實施例1之淨水器之剖面圖示於圖3。實施例1之淨水器為連續式淨水器，且為於水管之水龍頭之前端部直接安裝淨水器本體之水龍頭直連型之淨水器。實施例1之淨水器包括淨水器本體10、配置於淨水器本體10之內部且填充有實施例1A或實施例1B、參考例1之多孔質碳材料11之第1填充部12、及填充有棉13之第2填充部14。自水管之水龍頭排出之自來水自設置於淨水器本體10之流入口15通過多孔質碳材料11、棉13而自設置於淨水器本體10之流出口16排出。A cross-sectional view of the water purifier of Example 1 is shown in Fig. 3. The water purifier of Embodiment 1 is a continuous water purifier, and is a water purifier directly connected to the water purifier body directly connected to the front end of the water pipe faucet. The water purifier of the first embodiment includes a water purifier body 10, a first filling portion 12 which is disposed inside the water purifier body 10 and is filled with the porous carbon material 11 of the embodiment 1A or the embodiment 1B and the reference example 1, And the second filling portion 14 filled with the cotton 13. The tap water discharged from the faucet of the water pipe is discharged from the inflow port 15 provided in the water purifier body 10 through the porous carbon material 11 and the cotton 13 through the inlet 15 of the water purifier body 10.

將表示實施例1之污染物質除去板片部件之剖面構造之模式圖示於圖4。實施例1之污染物質除去板片部件包括實施例1A或實施例1B、參考例1之多孔質碳材料、及支持部件。具體而言，實施例1之污染物質除去板片部件具有於包含纖維素之支持部件(不織布2)與支持部件(不織布2)之間夾持有片狀之多孔質碳材料、即碳/聚合物複合體1之構 造。碳/聚合物複合體1包含實施例1A或實施例1B、參考例1之多孔質碳材料、及黏合劑，黏合劑例如包含羧基硝化纖維素。再者，亦可將污染物質除去板片部件設為將實施例1A或實施例1B、參考例1之多孔質碳材料塗佈於支持部件上、或者將實施例1之多孔質碳材料捏合於支持部件中之形態。A schematic diagram showing a cross-sectional structure of the pollutant removing sheet member of the first embodiment is shown in Fig. 4 . The pollutant removing sheet member of Example 1 includes the porous carbon material of Example 1A or Example 1B, Reference Example 1, and a supporting member. Specifically, the pollutant removing sheet member of the first embodiment has a sheet-like porous carbon material, that is, carbon/polymerized, between the supporting member (nonwoven fabric 2) containing cellulose and the supporting member (nonwoven fabric 2). Structure of matter complex 1 Made. The carbon/polymer composite 1 comprises the porous carbon material of Example 1A or Example 1B, Reference Example 1, and a binder, and the binder contains, for example, a carboxylated nitrocellulose. Further, the contaminant-removing sheet member may be obtained by applying the porous carbon material of Example 1A or Example 1B and Reference Example 1 to a support member, or kneading the porous carbon material of Example 1 to Supports the form in the part.

[實施例2][Embodiment 2]

實施例2為實施例1之變形。於實施例2中進行與氯之除去率相關之評估試驗。Embodiment 2 is a modification of Embodiment 1. An evaluation test relating to the removal rate of chlorine was carried out in Example 2.

於實施例2中之多孔質碳材料之製造中，藉由將源自植物之材料於400℃至1400℃下碳化後以酸或鹼進行處理而獲得多孔質碳材料。即，首先於惰性氣體中對稻殼實施加熱處理(預碳化處理)。具體而言，藉由將稻殼於氮氣流中於500℃下加熱5小時使其碳化，而獲得碳化物。再者，藉由進行此種處理，可減少或除去後續之碳化時可能生成之焦油成分。其後，將10克該碳化物加入至氧化鋁製之坩堝中，於氮氣流中(10升/分鐘)以5℃/分鐘之升溫速度使其升溫至800℃。繼而，於800℃下碳化1小時使其轉換為碳質物質(多孔質碳材料前驅物)後冷卻至室溫。再者，於碳化及冷卻中使氮氣持續流通。其次，藉由使該多孔質碳材料前驅物於46容積%之氫氟酸水溶液中浸漬一晚而進行酸處理後，使用水及乙醇清洗至pH值成為7為止。其次，於120℃下進行乾燥後，藉由於900℃下且於水蒸氣氣流中(3.5升/分鐘)中加熱3小時而進行活化處理，藉此可獲得實 施例2之多孔質碳材料。In the production of the porous carbon material in Example 2, a porous carbon material is obtained by subjecting a plant-derived material to carbonization at 400 ° C to 1400 ° C and then treating it with an acid or a base. That is, the rice husk is first subjected to heat treatment (pre-carbonization treatment) in an inert gas. Specifically, a carbide was obtained by carbonizing a rice husk by heating at 500 ° C for 5 hours in a nitrogen stream. Further, by performing such treatment, the tar component which may be generated upon subsequent carbonization can be reduced or removed. Thereafter, 10 g of this carbide was placed in a crucible made of alumina, and the temperature was raised to 800 ° C in a nitrogen stream (10 liter / min) at a temperature elevation rate of 5 ° C / min. Then, it was carbonized at 800 ° C for 1 hour to be converted into a carbonaceous substance (porous carbon material precursor), and then cooled to room temperature. Further, nitrogen gas is continuously circulated during carbonization and cooling. Next, the porous carbon material precursor was immersed in a 46% by volume aqueous solution of hydrofluoric acid for one night to carry out an acid treatment, and then washed with water and ethanol until the pH became 7. Next, after drying at 120 ° C, activation treatment was carried out by heating at 900 ° C for 3 hours in a steam gas stream (3.5 liter / minute), whereby The porous carbon material of Example 2.

測定實施例2中之濾材之比表面積及孔隙容積，結果獲得表1所示之結果。將實施例2之濾材粉碎進行粒度調整，而製成200網目未通過品。再者，製備具有2種粒度分佈之實施例2A及實施例2B之試樣。將使用有篩之粒度分佈測定結果示於表3。進而，自市售之淨水器中取出活性碳，將該等活性碳設為比較例2A、比較例2B及比較例2C而進行評估。又，將相同容積(2.0 cm3 )之第1填充部12中填充有各試樣時之質量(單位：克)示於表1，有時將第1填充部12中填充有各試樣時之填充比率稱為「填充率」。進而，將基於NLDFT法的具有於3 nm至20 nm之範圍內之孔隙徑之孔隙之容積之合計相對於直徑為1×10-9 m至5×10-7 m之孔隙之容積之合計(所有孔隙之容積總計)所占的容積比率示於表2。又，將汞滲法之測定結果示於以下。進而，將於120℃下乾燥12小時而得之試樣基於熱重量測定法(TG)法以乾燥空氣300毫升/分鐘加熱至800℃時的殘餘之灼燒餘物(殘留灰分)之測定結果示於以下。再者，亦一併表示實施例1、實施例7之多孔質碳材料之灼燒餘物(殘留灰分)之測定結果、及進行酸處理前之多孔質碳材料前驅物之灼燒餘物(殘留灰分)之測定結果。The specific surface area and pore volume of the filter medium in Example 2 were measured, and as a result, the results shown in Table 1 were obtained. The filter medium of Example 2 was pulverized and subjected to particle size adjustment to prepare a 200 mesh unfinished product. Further, samples of Example 2A and Example 2B having two particle size distributions were prepared. The results of particle size distribution measurement using a sieve are shown in Table 3. Further, activated carbon was taken out from a commercially available water purifier, and the activated carbons were evaluated in Comparative Example 2A, Comparative Example 2B, and Comparative Example 2C. In addition, the mass (unit: gram) when each sample is filled in the first filling portion 12 of the same volume (2.0 cm 3 ) is shown in Table 1, and the first filling portion 12 may be filled with each sample. The fill ratio is called the fill rate. Further, the total of the volumes of the pores having the pore diameters in the range of 3 nm to 20 nm based on the NLDFT method is the total of the volumes of the pores having a diameter of 1 × 10 -9 m to 5 × 10 -7 m ( The volume ratio of all the pore volumes is shown in Table 2. Further, the measurement results of the mercury infiltration method are shown below. Further, the measurement result of the residual burning residue (residual ash) when the sample was dried at 120 ° C for 12 hours and heated to 300 ° C in dry air at 300 ml/min by a thermogravimetric method (TG) method. Shown below. Further, the measurement results of the burning residue (residual ash) of the porous carbon material of Example 1 and Example 7, and the burning residue of the porous carbon material precursor before the acid treatment are also shown ( Determination of residual ash).

[汞滲法之測定結果][Measurement results of mercury infiltration method]

[灼燒餘物][burning residue]

於試驗中，以容積為2毫升之各試樣填充內徑為7.0 mm之玻璃管，使2.0毫克/升之濃度之氯水以400毫升/分鐘之流速於玻璃管內流動。繼而，將根據基於DPD(N,N-diethyl-1,4-phenylenediamine，N,N-二乙基-1,4-苯二胺)吸光光度法之除去率(%)=(原水測定值-通過水測定值)/原水測定值×100等方法而獲得之氯之除去率測定結果示於圖5。再者，將400毫升/分鐘之流量換算為空間速度(SV，Space Velocity)則如下所示。In the test, a glass tube having an inner diameter of 7.0 mm was filled with each sample having a volume of 2 ml, and chlorine water having a concentration of 2.0 mg/liter was flowed in the glass tube at a flow rate of 400 ml/min. Then, according to DPD (N, N-diethyl-1,4-phenylenediamine, N, N-diethyl-1,4-phenylenediamine), the removal rate (%) = (raw water measurement value - The measurement result of the chlorine removal rate obtained by the method of the water measurement value / raw water measurement value x 100 is shown in FIG. Furthermore, converting the flow rate of 400 ml/min into space velocity (SV, Space Velocity) is as follows.

SV=400×60(毫升/小時)/2 cm3 =12000小時-1 SV=400×60 (ml/hr)/2 cm 3 =12000 hours -1

根據圖5，實施例2A及實施例2B之包含多孔質碳材料之濾材具有明顯高於比較例2A、比較例2B、比較例2C之氯除去率。According to Fig. 5, the filter medium containing the porous carbon material of Example 2A and Example 2B had significantly higher chlorine removal rates than Comparative Example 2A, Comparative Example 2B, and Comparative Example 2C.

[實施例3][Example 3]

實施例3亦為實施例1之變形。於實施例3中進行與氯之除去率、1,1,1-三氯乙烷之除去率、2-氯-4,6-雙(乙胺基)-1,3,5-三(CAT)之除去率相關之評估試驗。除去率係藉由氣相層析分析法且根據下式而算出。使用實施例2A之多孔 質碳材料(200網目未通過品)作為構成實施例3之濾材之多孔質碳材料。再者，比較例3中使用與比較例2C相同之濾材。Embodiment 3 is also a modification of Embodiment 1. The removal rate with chlorine, the removal rate of 1,1,1-trichloroethane, 2-chloro-4,6-bis(ethylamino)-1,3,5-three were carried out in Example 3. Evaluation test for the removal rate of (CAT). The removal rate was calculated by gas chromatography analysis and according to the following formula. The porous carbon material of Example 2A (200 mesh unpenetrated product) was used as the porous carbon material constituting the filter medium of Example 3. Further, in Comparative Example 3, the same filter medium as in Comparative Example 2C was used.

除去率(%)=(原水測定值-通過水測定值)/原水測定值×100Removal rate (%) = (raw water measurement value - measured value by water) / raw water measurement value × 100

使用實施例3及比較例3之濾材，以容積為10毫升之各試樣填充內徑為10.0 mm之玻璃管，使2.0毫克/升之濃度之氯水、0.3毫克/升之濃度之1,1,1-三氯乙烷水溶液、0.003毫克/升之濃度之CAT水溶液以400毫升/分鐘之流速於玻璃管內流動。將氯、1,1,1-三氯乙烷、CAT之除去率示於圖6(A)、(B)及(C)。根據圖6(A)、(B)及(C)判斷出實施例3之包含多孔質碳材料之濾材具有明顯高於比較例3之除去率。再者，將400毫升/分鐘之流量換算為空間速度(SV)則如下所示。Using the filter materials of Example 3 and Comparative Example 3, a glass tube having an inner diameter of 10.0 mm was filled with each sample having a volume of 10 ml, and a concentration of chlorine of 2.0 mg/liter and a concentration of 0.3 mg/liter were made. An aqueous solution of 1,1-trichloroethane and a CAT aqueous solution having a concentration of 0.003 mg/liter were flowed through the glass tube at a flow rate of 400 ml/min. The removal rates of chlorine, 1,1,1-trichloroethane and CAT are shown in Figures 6(A), (B) and (C). According to FIGS. 6(A), (B) and (C), it was judged that the filter medium containing the porous carbon material of Example 3 had a significantly higher removal rate than that of Comparative Example 3. Furthermore, converting the flow rate of 400 ml/min into space velocity (SV) is as follows.

SV=400×60(毫升/小時)/10 cm3 =2400小時-1 SV = 400 × 60 (ml / hour) / 10 cm 3 = 2400 hours -1

[實施例4][Example 4]

於富營養化之湖沼或池中，藍藻類(微囊藻屬等)以暑期為中心進行異常增殖，形成如水之表面鋪上綠色之粉般之較厚之層，其被稱為水藻。眾所周知該藍藻類產生對人體有害之毒素，於眾多毒素中成為微囊藻毒素LR之毒素尤其需要防範。若微囊藻毒素LR進入至生物體內，則肝臟受到較大之損傷，於利用小鼠之實驗中亦報告有其毒性。釋放微囊藻毒素LR之有毒水藻產生於澳洲或歐洲、美國之湖泊、亞洲各地。於受害較大之中國之湖泊中，大量產生之水藻一年之內不會消失。而且，由於湖水用於飲用水或農 業用水，故而於湖沼中藍藻類生出之毒素於人類之飲用水之確保方面成為問題，強烈期待將其解決。In the eutrophic lakes or ponds, cyanobacteria (Microcystis, etc.) proliferate abnormally around the summer, forming a thick layer like green powder on the surface of water, which is called algae. It is well known that the cyanobacteria produce toxins harmful to the human body, and it is particularly necessary to prevent the toxins of microcystins LR among many toxins. If microcystin LR enters the organism, the liver is greatly damaged, and its toxicity is also reported in experiments using mice. The toxic algae that release microcystins LR are produced in Australia or Europe, lakes in the United States, and throughout Asia. In the lakes of the more affected China, the large amount of algae produced will not disappear within a year. Moreover, because the lake is used for drinking water or agriculture Industrial water, so the toxins produced by cyanobacteria in the lakes are a problem in ensuring the drinking water of human beings, and it is strongly expected to solve them.

於實施例4中，對微囊藻毒素LR(數量平均分子量：994)之吸附進行評估。以與實施例1中說明之方法大概相同之方法獲得構成實施例4之濾材之多孔質碳材料。具體而言，於實施例4中，將活化處理設為於900℃下於水蒸氣氣流中(2.5升/分鐘)加熱3小時之處理。除此點以外，均以與實施例1中說明之方法相同之方法獲得。測定實施例4中之濾材之比表面積及孔隙容積，結果獲得表1所示之結果。 又，將基於NLDFT法的具有於3 nm至20 nm之範圍內之孔隙徑之孔隙之容積之合計相對於直徑為1×10-9 m至5×10-7 m之孔隙之容積之合計(容積A，所有孔隙之容積總計)所占的容積比率示於表2。再者，實施例4中之濾材為60網目通過、200網目未通過品。又，使用和光純藥工業股份有限公司製造之粒狀活性碳(60網目通過、200網目未通過品)作為比較例4。In Example 4, the adsorption of microcystins LR (number average molecular weight: 994) was evaluated. The porous carbon material constituting the filter medium of Example 4 was obtained in substantially the same manner as the method described in Example 1. Specifically, in Example 4, the activation treatment was carried out by heating at 900 ° C for 3 hours in a steam gas stream (2.5 liter / minute). Except for this point, it was obtained in the same manner as the method described in Example 1. The specific surface area and pore volume of the filter medium in Example 4 were measured, and as a result, the results shown in Table 1 were obtained. Further, the total of the volumes of the pores having the pore diameters in the range of 3 nm to 20 nm based on the NLDFT method is the total of the volumes of the pores having a diameter of 1 × 10 -9 m to 5 × 10 -7 m ( The volume ratio of volume A, the total volume of all pores) is shown in Table 2. Further, the filter medium of Example 4 was 60 mesh passages and 200 mesh failure products. Further, as the comparative example 4, granular activated carbon (60 mesh passage, 200 mesh failed product) manufactured by Wako Pure Chemical Industries Co., Ltd. was used.

使用實施例4及比較例4之濾材，藉由使用有紫外可見分光光度計之比色法而求出反應前後之溶液之微囊藻毒素濃度，算出除去率。將其結果示於圖7，實施例4之包含多孔質碳材料之濾材具有明顯高於比較例4之除去率。Using the filter materials of Example 4 and Comparative Example 4, the microcystin concentration of the solution before and after the reaction was determined by a colorimetric method using an ultraviolet-visible spectrophotometer, and the removal rate was calculated. The results are shown in Fig. 7. The filter medium containing the porous carbon material of Example 4 had a significantly higher removal rate than that of Comparative Example 4.

[實施例5][Example 5]

於實施例5中進行粒徑依存性之評估。使用實施例1中之多孔質碳材料(60網目通過、200網目未通過品)作為構成實施例5之濾材之多孔質碳材料。又，將為實施例1中之多孔 質碳材料且為200網目通過品設為參考例5。進而，使用比較例4之粒狀活性碳(60網目通過、200網目未通過品)作為比較例5A，使用將比較例4之粒狀活性碳粉碎而得之200網目通過品作為比較例5B。The evaluation of the particle size dependence was carried out in Example 5. The porous carbon material (60 mesh passage, 200 mesh failure) in Example 1 was used as the porous carbon material constituting the filter medium of Example 5. Also, it will be the porous in Example 1. The carbonaceous material and 200 mesh passages were referred to as Reference Example 5. Further, as the comparative example 5A, the granular activated carbon of Comparative Example 4 (60 mesh passage, 200 mesh unpenetrated product) was used, and the 200 mesh passage product obtained by pulverizing the granular activated carbon of Comparative Example 4 was used as Comparative Example 5B. .

使用實施例5、參考例5、比較例5A及比較例5B之濾材作為試樣，向50毫升之螺旋管中加入10毫克試樣及50毫升吲哚溶液(3×10-4 莫耳/升)，基於對1小時後之吲哚吸附量進行定量之方法評估粒徑依存性。將其結果示於圖8，判斷出實施例5、參考例5之包含多孔質碳材料之濾材與比較例5A、比較例5B相比並無粒徑依存性。Using the filter materials of Example 5, Reference Example 5, Comparative Example 5A and Comparative Example 5B as a sample, 10 mg of the sample and 50 ml of hydrazine solution (3 × 10 -4 mol/liter were added to a 50 ml spiral tube). The particle size dependence was evaluated based on the method of quantifying the amount of ruthenium adsorption after one hour. The results are shown in Fig. 8. It was found that the filter medium containing the porous carbon material of Example 5 and Reference Example 5 had no particle diameter dependency as compared with Comparative Example 5A and Comparative Example 5B.

[實施例6][Embodiment 6]

以先前之椰殼或石油瀝青為原料之活性碳用於以淨水用等之過濾器部件為首之功能性食品、化妝品等，但該等活性碳之礦物含量較少，不適於調整礦物向水等中之釋放量之目的。Activated carbon based on the previous coconut shell or petroleum pitch is used for functional foods, cosmetics, etc., which are mainly used for filter components such as water purification, but these activated carbons have a small mineral content and are not suitable for adjusting minerals to water. The purpose of the release amount.

實施例6係關於本發明之第5態樣~第8態樣之濾材。實施例6之濾材包含如下多孔質碳材料：藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，藉由BJH法所得之孔隙之容積為0.1 cm3 /克以上，且以含有選自由鈉、鎂、鉀及鈣所組成之群中之至少1種成分之植物為原料。或者，實施例6之濾材包含如下多孔質碳材料：藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，藉由非定域化密度泛函數法求出之直徑為1×10-9 m至5×10-7 m之孔隙之容積之合計為0.1 cm3 /克以上、較佳為0.2 cm3 /克以上，且以含有 選自由鈉、鎂、鉀及鈣所組成之群中之至少1種成分之植物為原料。或者，實施例6之濾材包含如下多孔質碳材料：藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，於藉由非定域化密度泛函數法求出之孔隙徑分佈中在3 nm至20 nm之範圍內具有至少1個峰值，具有於3 nm至20 nm之範圍內之孔隙徑之孔隙之容積之合計所占之比率為所有孔隙之容積總計之0.1以上，且以含有選自由鈉、鎂、鉀及鈣所組成之群中之至少1種成分之植物為原料。或者，實施例6之濾材包含如下多孔質碳材料：藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，藉由汞滲法所得之孔隙之容積為1.0 cm3 /克以上，且以含有選自由鈉、鎂、鉀及鈣所組成之群中之至少1種成分之植物為原料。Embodiment 6 relates to a filter material according to a fifth aspect to an eighth aspect of the present invention. The filter medium of Example 6 comprises the following porous carbon material: the specific surface area obtained by the nitrogen BET method has a value of 1 × 10 2 m 2 /g or more, and the volume of the pore obtained by the BJH method is 0.1 cm 3 /g or more. And a plant containing at least one component selected from the group consisting of sodium, magnesium, potassium, and calcium is used as a raw material. Alternatively, the filter medium of Example 6 comprises a porous carbon material having a specific surface area obtained by a nitrogen BET method of 1 × 10 2 m 2 /g or more, which is obtained by a delocalized density functional method. The volume of the pores having a diameter of from 1 × 10 -9 m to 5 × 10 -7 m is 0.1 cm 3 /g or more, preferably 0.2 cm 3 /g or more, and contains a substance selected from the group consisting of sodium, magnesium, potassium and A plant having at least one component selected from the group consisting of calcium is used as a raw material. Alternatively, the filter medium of Example 6 comprises a porous carbon material having a specific surface area obtained by a nitrogen BET method of 1 × 10 2 m 2 /g or more, which is obtained by a delocalized density functional method. The pore diameter distribution has at least one peak in the range of 3 nm to 20 nm, and the ratio of the volume of the pores having the pore diameter in the range of 3 nm to 20 nm accounts for the total volume of all the pores. 0.1 or more, and a plant containing at least one component selected from the group consisting of sodium, magnesium, potassium, and calcium is used as a raw material. Alternatively, the filter medium of Example 6 comprises a porous carbon material having a specific surface area obtained by a nitrogen BET method of 1 × 10 2 m 2 /g or more, and a volume of pores obtained by a mercury infiltration method of 1.0 cm 3 . More than gram, and a plant containing at least one component selected from the group consisting of sodium, magnesium, potassium, and calcium is used as a raw material.

於實施例6中，多孔質碳材料係以含有選自由鈉(Na)、鎂(Mg)、鉀(K)及鈣(Ca)所組成之群中之至少1種成分之植物為原料。藉由使用此種植物原料，於用作濾材時，礦物成分大多會自多孔質碳材料溶出至過濾水中，其結果，可進行水之硬度之控制。而且，於該情形時，向硬度為0.1以下之水(試驗用水)50毫升中添加1克濾材，經過6小時後之硬度成為5以上。In the sixth embodiment, the porous carbon material is made of a plant containing at least one component selected from the group consisting of sodium (Na), magnesium (Mg), potassium (K), and calcium (Ca). When such a plant material is used, when it is used as a filter material, most of the mineral components are eluted from the porous carbon material into the filtered water, and as a result, the hardness of the water can be controlled. Further, in this case, 1 g of the filter medium was added to 50 ml of water (test water) having a hardness of 0.1 or less, and the hardness after 5 hours passed was 5 or more.

更具體而言，於實施例6中，使用橘子皮(實施例6A)、橙子皮(實施例6B)、葡萄柚皮(實施例6C)等柑橘類之皮、香蕉皮(實施例6D)作為原料。又，使用Kuraray Chemical股份有限公司製造之Kuraraycoal GW作為比較例6。More specifically, in Example 6, citrus peel and banana peel (Example 6D) such as orange peel (Example 6A), orange peel (Example 6B), and grapefruit peel (Example 6C) were used as raw materials. . Further, Kuraraycoal GW manufactured by Kuraray Chemical Co., Ltd. was used as Comparative Example 6.

於構成實施例6之濾材之多孔質碳材料之製造中，將上 述各種植物原料於120℃下進行24小時乾燥處理。其後，於500℃之氮氣流中實施3小時預碳化處理。其次，於800℃下進行1小時煅燒處理後冷卻至室溫，使用乳缽進行粉碎處理。為方便起見，將如此獲得之試樣(碳質物質、多孔質碳材料前驅物)稱為實施例6a、實施例6b、實施例6c及實施例6d之試樣。其後，藉由使各試樣於濃鹽酸中浸漬24小時後清洗至清洗液成為中性為止，而獲得實施例6a'、實施例6b'、實施例6c'及實施例6d'之試樣。其次，藉由將實施例6a'、實施例6b'、實施例6c'及實施例6d'之試樣於900℃下於水蒸氣氣流中進行1小時活化處理，可獲得實施例6A、實施例6B、實施例6C及實施例6D之包含多孔質碳材料之濾材。In the manufacture of the porous carbon material constituting the filter medium of Example 6, The various plant materials were dried at 120 ° C for 24 hours. Thereafter, a pre-carbonization treatment was carried out for 3 hours in a nitrogen stream at 500 °C. Next, the calcination treatment was carried out at 800 ° C for 1 hour, and then cooled to room temperature, and pulverization treatment was carried out using a mortar. For the sake of convenience, the sample (carbonaceous material, porous carbon material precursor) thus obtained is referred to as a sample of Example 6a, Example 6b, Example 6c, and Example 6d. Thereafter, samples of Examples 6a', 6b', 6c' and 6d' were obtained by immersing each sample in concentrated hydrochloric acid for 24 hours and then washing until the cleaning liquid became neutral. . Next, Example 6A and Examples were obtained by subjecting the samples of Example 6a', Example 6b', Example 6c' and Example 6d' to activation treatment at 900 ° C for 1 hour in a steam stream. 6B, the filter material of the porous carbon material of Example 6C and Example 6D.

將實施例6A、實施例6B、實施例6C及實施例6D之試樣、以及比較例6之試樣之組成分析結果示於以下之表4。又，將實施例6a、實施例6b、實施例6c及實施例6d之試樣、以及實施例6a'、實施例6b'、實施例6c'及實施例6d'之多孔質碳材料之X射線繞射結果示於圖9之(A)~(D)。再者，實施例6A、實施例6B、實施例6C及實施例6D之濾材均設為200網目通過品。又，測定比表面積及孔隙容積，結果獲得表1及圖10(A)、(B)所示之結果。又，將基於NLDFT法的具有於3 nm至20 nm之範圍內之孔隙徑之孔隙之容積之合計相對於直徑為1×10-9 m至5×10-7 m之孔隙之容積之合計(容積A，所有孔隙之容積總計)所占的容積比率示於表2。進而，將表示實施例6A、實施例6B、實施例 6C及實施例6D之濾材、以及比較例6之藉由非定域化密度泛函數法求出之孔隙徑分佈之測定結果之圖表示於圖11。The composition analysis results of the samples of Example 6A, Example 6B, Example 6C and Example 6D, and the sample of Comparative Example 6 are shown in Table 4 below. Further, X-rays of the porous carbon materials of Examples 6a, 6b, 6c and 6d, and Examples 6a', 6b', 6c' and 6d' were used. The diffraction results are shown in (A) to (D) of Fig. 9. Further, the filter materials of Example 6A, Example 6B, Example 6C, and Example 6D were all set to 200 mesh products. Further, the specific surface area and the pore volume were measured, and as a result, the results shown in Table 1 and Figs. 10(A) and (B) were obtained. Further, the total of the volumes of the pores having the pore diameters in the range of 3 nm to 20 nm based on the NLDFT method is the total of the volumes of the pores having a diameter of 1 × 10 -9 m to 5 × 10 -7 m ( The volume ratio of volume A, the total volume of all pores) is shown in Table 2. Further, the graphs showing the measurement results of the pore diameter distributions obtained by the non-localized density functional method of the filter materials of Example 6A, Example 6B, Example 6C, and Example 6D and Comparative Example 6 are shown. In Figure 11.

根據表4判斷出實施例6A、實施例6B、實施例6C及實施例6D之試樣與比較例6之試樣相比含有較多之礦物成分。又，根據X射線繞射結果，自實施例6a'、實施例6b'、實施例6c'及實施例6d'之濾材中未觀測到於實施例6a、實施例6b、實施例6c及實施例6d之試樣中觀察到之源自礦物成分之結晶性峰值。根據以上內容，認為礦物成分藉由利用濃鹽酸之酸處理而局部地暫時被除去，但藉由活化處理而使濾材內部之礦物成分再次明顯化。According to Table 4, it was judged that the samples of Example 6A, Example 6B, Example 6C, and Example 6D contained a larger amount of mineral components than the sample of Comparative Example 6. Further, according to the X-ray diffraction results, Example 6a, Example 6b, Example 6c, and Example were not observed from the filter materials of Example 6a', Example 6b', Example 6c', and Example 6d'. The crystallographic peak derived from the mineral component was observed in the 6d sample. According to the above, it is considered that the mineral component is partially temporarily removed by treatment with concentrated hydrochloric acid, but the mineral component inside the filter medium is reappared by the activation treatment.

使用實施例6A、實施例6B、實施例6C及實施例6D之試樣、以及比較例6之試樣，將各試樣以1克/50毫升之比率添加至作為純水之試驗用水(硬度：<0.066)中，攪拌6小時後進行過濾，藉由ICP-AES(Inductively Coupled Plasma-Atomic Emission Spectrometer，感應耦合電漿原子發射光譜儀)對濾液中所含之各種礦物量進行定量。表5表示自各試樣獲得之濾液中之礦物量及濾液之硬度。再者，硬度(毫克/升)係作為鈣濃度(毫克/升)×2.5+鎂濃度(毫克/升)×4.1而算出。作為參考，亦表示有按照世界衛生組織(WHO，World Health Organization)之基準(軟水：0以上且未達60，中等程度之軟水(中硬水)：60以上且未達120，硬水：120以上且未達180，非常硬水：180以上)之水之分類。Using the samples of Example 6A, Example 6B, Example 6C and Example 6D, and the sample of Comparative Example 6, each sample was added to the test water as pure water at a ratio of 1 g / 50 ml (hardness). In <0.066), after stirring for 6 hours, filtration was carried out, and the amount of various minerals contained in the filtrate was quantified by ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectrometer). Table 5 shows the amount of minerals in the filtrate obtained from each sample and the hardness of the filtrate. Further, the hardness (mg/L) was calculated as the calcium concentration (mg/L) × 2.5 + magnesium concentration (mg/L) × 4.1. For reference, it also indicates that according to the World Health Organization (WHO, World Health Organization) (soft water: 0 or more and less than 60, moderate soft water (medium hard water): 60 or more and less than 120, hard water: 120 or more The classification of water that is less than 180, very hard water: 180 or more.

根據表5，於實施例6之各試樣中可確認到較比較例6高 之礦物溶出特性，表示實施例6之包含多孔質碳材料之濾材適於濾液之硬度之調整。又，判斷出可藉由所使用之植物原料將所獲得之濾液之硬度調整為軟水~中硬水~硬水~非常硬水。According to Table 5, it was confirmed in each of the samples of Example 6 that it was higher than Comparative Example 6. The mineral elution property indicates that the filter medium containing the porous carbon material of Example 6 is suitable for the adjustment of the hardness of the filtrate. Further, it was judged that the hardness of the obtained filtrate can be adjusted from soft water to medium hard water to hard water to very hard water by the plant material used.

[實施例7][Embodiment 7]

實施例7係關於本揭示之第9態樣~第15態樣之濾材。實施例7之目的在於除去於水環境中大量排出之合成洗劑成分之十二烷基苯磺酸鹽(具體而言為直鏈十二烷基苯磺酸 鈉)、大量使用之農藥之殺菌劑百菌清(TPN(Tetrachloroisophthalonitrile，四氯異苯腈)，C8 Cl4 N)及殺蟲劑二氯松(DDVP(Dimethyl Dichloro Vinyl Phosphate，二甲基二氯乙烯基磷酸酯)，C4 H7 Cl2 O4 P)、自水管等溶出之可溶性鉛、作為自來水中之典型污染物質之游離殘留氯、以及因氯消毒而作為副產物產生之多種有機鹵化合物類(包括自腐植質產生之有機鹵化合物)。Embodiment 7 is a filter material according to the ninth aspect to the fifteenth aspect of the present disclosure. The purpose of Example 7 is to remove the dodecylbenzenesulfonate (specifically, sodium linear dodecylbenzenesulfonate) of the synthetic detergent component which is discharged in a large amount in an aqueous environment, and to sterilize the pesticide used in a large amount. Chlorophyll (TPN (Tetrachloroisophthalonitrile), C 8 Cl 4 N) and insecticide Diclofen (DDVP (Dimethyl Dichloro Vinyl Phosphate), C 4 H 7 Cl 2 O 4 P), soluble lead dissolved from a water pipe, free residual chlorine as a typical pollutant in tap water, and various organic halogen compounds (including self-humus) produced as a by-product due to chlorine disinfection Organic halogen compound).

實施例7中，利用以下方法製造多孔質碳材料。又，使用Kuraraycoal GW作為比較例7。In Example 7, a porous carbon material was produced by the following method. Further, Kuraraycoal GW was used as Comparative Example 7.

於實施例7中之多孔質碳材料之製造中，藉由將源自植物之材料於400℃至1400℃下碳化後以鹼進行處理而獲得多孔質碳材料。即，首先於惰性氣體中對稻殼實施加熱處理(預碳化處理)。具體而言，藉由將稻殼於氮氣流中於500℃下加熱5小時使其碳化，而獲得碳化物。再者，藉由進行此種處理，可減少或除去後續之碳化時可能生成之焦油成分。其後，將10克該碳化物加入至氧化鋁製之坩堝中，於氮氣流中(10升/分鐘)以5℃/分鐘之升溫速度使其升溫至800℃。繼而，於800℃下碳化1小時使其轉換為碳質物質(多孔質碳材料前驅物)後冷卻至室溫。再者，於碳化及冷卻中使氮氣持續流通。其次，藉由使該多孔質碳材料前驅物於80℃下於10質量%之氫氧化鈉水溶液中浸漬一晚而進行鹼處理後，使用水及乙醇清洗至pH值成為7為止。其次，於120℃下進行乾燥後，藉由於900℃下於水蒸氣氣流中(2.5升/分鐘)加熱3小時而進行活化處理，藉此可獲得 實施例7之多孔質碳材料。In the production of the porous carbon material in Example 7, a porous carbon material is obtained by subjecting a plant-derived material to carbonization at 400 ° C to 1400 ° C and then treating it with a base. That is, the rice husk is first subjected to heat treatment (pre-carbonization treatment) in an inert gas. Specifically, a carbide was obtained by carbonizing a rice husk by heating at 500 ° C for 5 hours in a nitrogen stream. Further, by performing such treatment, the tar component which may be generated upon subsequent carbonization can be reduced or removed. Thereafter, 10 g of this carbide was placed in a crucible made of alumina, and the temperature was raised to 800 ° C in a nitrogen stream (10 liter / min) at a temperature elevation rate of 5 ° C / min. Then, it was carbonized at 800 ° C for 1 hour to be converted into a carbonaceous substance (porous carbon material precursor), and then cooled to room temperature. Further, nitrogen gas is continuously circulated during carbonization and cooling. Then, the porous carbon material precursor was immersed in a 10% by mass aqueous sodium hydroxide solution at 80 ° C for one night, and then alkali-treated, and then washed with water and ethanol until the pH became 7. Next, after drying at 120 ° C, activation treatment is carried out by heating at 900 ° C for 3 hours in a steam stream (2.5 liter / minute). The porous carbon material of Example 7.

將實施例7及比較例7之試樣之粒度分佈測定結果示於表3。又，將實施例7及比較例7之試樣之比表面積及孔隙容積之測定結果示於以下之表6及表7。表6及表7之測定項目、單位與表1及表2相同。進而，將汞滲法之測定結果示於表8。The particle size distribution measurement results of the samples of Example 7 and Comparative Example 7 are shown in Table 3. Further, the measurement results of the specific surface area and the pore volume of the samples of Example 7 and Comparative Example 7 are shown in Tables 6 and 7 below. The measurement items and units in Tables 6 and 7 are the same as Tables 1 and 2. Further, the measurement results of the mercury infiltration method are shown in Table 8.

對實施例7及比較例7之試樣2 cm3 進行抽樣，並儲存於帶不鏽鋼網之管柱中。繼而，製備每1升水中分別溶解有Samples 2 cm 3 of Example 7 and Comparative Example 7 were sampled and stored in a column with a stainless steel mesh. Then, the preparation is dissolved in 1 liter of water.

(A)0.9毫克十二烷基苯磺酸鈉(A) 0.9 mg of sodium dodecylbenzene sulfonate

(B)6.0微克百菌清(B) 6.0 micrograms of chlorothalonil

(C)6.0微克二氯松(C) 6.0 micrograms of diclofenac

(D)6微克(以鉛換算)溶解性鉛(具體而言為醋酸鉛)(D) 6 micrograms (in terms of lead) soluble lead (specifically lead acetate)

(E)0.2毫克(以氯換算)作為游離氯之次氯酸鈉(E) 0.2 mg (in terms of chlorine) sodium hypochlorite as free chlorine

(F)濃度為130±20微克/升(以氯換算)之作為總有機鹵素之TOX(Total Organic Halides，總有機鹵化物) 之溶液，以流量40毫升/分鐘使其通過2 cm3 之各試樣。而且，測定通水前後之濃度，算出除去率。再者，流量40毫升/分鐘對應於以下之空間速度(SV)。(F) A solution of TOX (Total Organic Halides) as a total organic halogen at a concentration of 130 ± 20 μg/L (in terms of chlorine), passing it at a flow rate of 40 ml/min for 2 cm 3 Sample. Further, the concentration before and after the water flow was measured, and the removal rate was calculated. Further, the flow rate of 40 ml/min corresponds to the following space velocity (SV).

又，製備每1升水中分別溶解有Moreover, the preparation is dissolved in 1 liter of water, respectively.

(A)0.9毫克十二烷基苯磺酸鈉(A) 0.9 mg of sodium dodecylbenzene sulfonate

(B)6微克百菌清(B) 6 micrograms of chlorothalonil

(E)2.0毫克(以氯換算)作為游離氯之次氯酸鈉之溶液，以流量240毫升/分鐘使其通過2 cm3 之各試樣。而且，測定通水前後之濃度，算出除去率。再者，流量240毫升/分鐘對應於以下之空間速度(SV)。(E) 2.0 mg (in terms of chlorine) as a solution of sodium chloride of free chlorine, which was passed through a sample of 2 cm 3 at a flow rate of 240 ml/min. Further, the concentration before and after the water flow was measured, and the removal rate was calculated. Further, the flow rate of 240 ml/min corresponds to the following space velocity (SV).

流量40毫升/分鐘：SV=40×60(毫升/小時)/2 cm3 =1200小時-1 Flow rate 40 ml / min: SV = 40 × 60 (ml / hour) / 2 cm 3 = 1200 hours -1

流量240毫升/分鐘：SV=240×60(毫升/小時)/2 cm3 =7200小時-1 Flow rate of 240 ml / min: SV = 240 × 60 (ml / hr) / 2 cm 3 = 7200 hr⁻¹

而且，基於單元吸光度法進行十二烷基苯磺酸鈉之除去率測定，基於帶電子捕獲檢測器之氣相層析(ECD-GC，Electron Capture Detector-Gas Chromatography)法進行百菌清及二氯松之除去率測定，基於感應耦合電漿-質量分析(ICP/MS，Inductive Coupled Plasma-Mass Spectrometry)法進行溶解性鉛之除去率測定，基於單元吸光度法進行游離氯之除去率測定，基於離子層析法進行總有機鹵素之除去率測定。Moreover, the removal rate of sodium dodecylbenzenesulfonate is determined based on the unit absorbance method, and the chlorothalonil and the second are performed based on an electrophoresis detector-based gas chromatography (ECD-GC, Electron Capture Detector-Gas Chromatography) method. Determination of the removal rate of the chlorinated pine, the determination of the removal rate of the dissolved lead by the inductive coupled plasma-mass spectrometry (ICP/MS) method, and the determination of the removal rate of the free chlorine based on the unit absorbance method, based on The total organic halogen removal rate was measured by ion chromatography.

將十二烷基苯磺酸鈉(DBS，Dodecyl Benzene Sulfonate)之除去率測定結果示於圖12(A)及(B)，將百菌清(TPN)之 除去率測定結果示於圖13(A)及(B)，將二氯松(DDVP)之除去率測定結果示於圖14，將溶解性鉛之除去率測定結果示於圖15，將游離氯之除去率測定結果示於圖16(A)及(B)，將總有機鹵素之除去率測定結果示於圖17。於所有中均顯示實施例7之除去率較比較例7高。The results of the removal rate of sodium dodecylbenzenesulfonate (DBS, Dodecyl Benzene Sulfonate) are shown in Fig. 12 (A) and (B), and chlorothalonil (TPN) was used. The results of the removal rate measurement are shown in Figs. 13(A) and (B), the measurement results of the removal rate of diclofenac (DDVP) are shown in Fig. 14, and the results of the measurement of the removal rate of soluble lead are shown in Fig. 15, and free chlorine is shown. The measurement results of the removal rate are shown in Fig. 16 (A) and (B), and the measurement results of the removal rate of the total organic halogen are shown in Fig. 17 . The removal rate of Example 7 was shown to be higher than that of Comparative Example 7 in all of them.

即，實施例7之濾材係於將含有分子量為1×102 至1×105 之物質1微克/升之水於空間速度為1200小時-1 下連續進行48小時通液時，直至該物質之除去率達到80%為止之時間為使用椰殼活性碳時之直至該物質之除去率達到80%為止之時間的2倍以上。That is, the filter medium of Example 7 is obtained by continuously passing water of 1 μg/L of a substance having a molecular weight of 1 × 10 2 to 1 × 10 5 at a space velocity of 1200 hr -1 for 48 hours until the substance The time until the removal rate reached 80% was twice or more the time until the removal rate of the substance reached 80% when the coconut shell activated carbon was used.

又，實施例7之濾材係於將含有0.9毫克/升十二烷基苯磺酸鹽之水於空間速度為1200小時-1 下連續進行25小時通液時，十二烷基苯磺酸鹽之除去率為10%以上。Further, the filter medium of Example 7 is a solution of dodecylbenzenesulfonate when a water containing 0.9 mg/liter of dodecylbenzenesulfonate is continuously passed for 25 hours at a space velocity of 1200 hours -1 . The removal rate is 10% or more.

又，實施例7之濾材係於將含有6微克/升百菌清之水於空間速度為1200小時-1 下連續進行50小時通液時，百菌清之除去率為60%以上。Further, in the filter medium of Example 7, when the water containing 6 μg/L of chlorothalonil was continuously passed for 50 hours at a space velocity of 1200 hr -1 , the removal rate of chlorothalonil was 60% or more.

又，實施例7之濾材係於將含有6微克/升二氯松之水於空間速度為1200小時-1 下連續進行25小時通液時，二氯松之除去率為60%以上。Further, in the filter medium of Example 7, when the water containing 6 μg/L of diclofen was continuously passed for 25 hours at a space velocity of 1200 hr -1 , the removal rate of diclosan was 60% or more.

又，實施例7之濾材係於將含有6微克/升溶解性鉛之水於空間速度為1200小時-1 下連續進行25小時通液時，溶解性鉛之除去率為30%以上。Further, in the filter medium of Example 7, when the water containing 6 μg/liter of soluble lead was continuously passed through at a space velocity of 1200 hr -1 for 25 hours, the removal rate of the soluble lead was 30% or more.

又，實施例7之濾材係於將含有0.2毫克/升游離氯之水於空間速度為1200小時-1 下連續進行50小時通液時，游離氯 之除去率為70%以上。Further, the filter medium of Example 7 was obtained by continuously flowing water containing 0.2 mg/liter of free chlorine at a space velocity of 1200 hr -1 for 50 hours, and the removal ratio of free chlorine was 70% or more.

又，實施例7之濾材係於將含有以氯換算為130微克/升總有機鹵素之水於空間速度1200小時-1 下連續進行5小時通液時，總有機鹵素之除去率為45%以上。Further, the filter medium of Example 7 was obtained by continuously flowing water containing 130 μg/L of total organic halogen in terms of chlorine at a space velocity of 1200 hr -1 for 5 hours, and the total organic halogen removal rate was 45% or more. .

再者，根據十二烷基苯磺酸鈉(DBS)之除去率測定結果，於SV=1200小時-1 下，實施例7之濾材雖填充率僅為比較例7之活性碳之約27%，但維持較比較例7之活性碳高之除去率，於通水約5小時下顯示出100%之除去率，於通水約27小時下呈現出50%以上之除去率。與此相對，比較例7之活性碳於通水後不久除去率便快速降低。認為其原因在於僅具有較小之孔隙之比較例7之活性碳中分子量較大之DBS之吸附速度較慢。而且，根據試驗之結果推定為：於實施例7中，於使用包含實施例7之濾材150毫升之固定型淨水器(以下於方便上稱為『固定型淨水器-A』)且設為含有0.2毫克/升之DBS之水之情形時，假設以3.0升/分鐘之流速1天過濾25升時，約18個月可將100% DBS除去。又，於SV=7200小時-1 下亦維持較比較例7之活性碳高之除去率。而且，推定為：於假設將含有0.2毫克/升之DBS之水以1.8升/分鐘之流速1天過濾15升之情形時，使用包含實施例7之濾材15毫升之固定型淨水器(以下於方便上稱為『固定型淨水器-B』)，約4個月可將50%以上DBS除去。Further, according to the measurement result of the removal rate of sodium dodecylbenzenesulfonate (DBS), the filling rate of the filter medium of Example 7 was only about 27% of that of Comparative Example 7 at SV = 1,200 hr -1 . However, the removal rate higher than that of the activated carbon of Comparative Example 7 was maintained, and the removal rate of 100% was exhibited in about 5 hours of passing water, and the removal rate was 50% or more in about 27 hours of passing water. On the other hand, the removal rate of the activated carbon of Comparative Example 7 was rapidly decreased shortly after the passage of water. The reason for this is considered to be that the adsorption rate of the DBS having a larger molecular weight in the activated carbon of Comparative Example 7 having only a smaller pore is slower. Further, it is estimated from the results of the test that, in the seventh embodiment, a fixed type water purifier including 150 ml of the filter medium of the seventh embodiment (hereinafter referred to as "fixed type water purifier-A" is conveniently used) In the case of water containing 0.2 mg/liter of DBS, it is assumed that 100% DBS can be removed in about 18 months when 25 liters of filtration is applied at a flow rate of 3.0 liter/min. Further, the removal rate higher than that of the activated carbon of Comparative Example 7 was maintained at SV = 7,200 hr -1 . Further, it is presumed that assuming that a water containing 0.2 mg/liter of DBS is filtered by 15 liters at a flow rate of 1.8 liter/min for 15 days, a fixed type water purifier comprising 15 ml of the filter material of Example 7 is used (hereinafter For convenience, it is called "fixed water purifier-B", and more than 50% of DBS can be removed in about 4 months.

又，根據百菌清(TPN)之除去率測定結果，於SV=1200小時-1 下，實施例7之濾材與比較例7之活性碳相比較高地維持TPN之除去率，直至比較例7之活性碳之通水20小時 等值之2.05倍的約50小時為止除去率為80%以上。認為上述情況係由於TPN之分子量較大為265.9，故而吸附速度較快之實施例7之濾材與比較例7之活性碳相比較為有利，又，由於TPN對水之溶解度較小，故而吸附性較高，因此長時間維持較高之除去率。而且，根據該試驗之結果推定為：於實施例7中，於使用固定型淨水器-A且假設將含有6.0微克/升之TPN之水以3.0升/分鐘之流速1天過濾25升之情形時，約1年可將80%以上TNP除去。另一方面，於SV=7200小時-1 下，雖除去率較SV=1200小時-1 之情形低，但於假設將含有6.0微克/升之TPN之水以1.8升/分鐘之流速1天過濾15升之情形時，使用固定型淨水器-B約7個月可將50%以上TNP除去。Further, according to the measurement result of the removal rate of chlorothalonil (TPN), the filter material of Example 7 maintained the removal rate of TPN higher than that of the activated carbon of Comparative Example 7 at SV = 1,200 hr -1 until the comparative example 7 was used. The removal rate of the activated carbon by water of 2.05 times the equivalent of 20 hours was about 80% or more. It is considered that the above situation is because the molecular weight of the TPN is as large as 265.9, so that the filter material of the seventh embodiment having a faster adsorption speed is more advantageous than the activated carbon of the comparative example 7, and the solubility of the TPN to water is small, so the adsorption property is Higher, so maintain a higher removal rate for a long time. Further, based on the results of the test, it was presumed that in Example 7, the fixed type water purifier-A was used and it was assumed that water containing 6.0 μg/liter of TPN was filtered at a flow rate of 3.0 liter/min for 25 days. In the case, more than 80% of TNPs can be removed in about 1 year. On the other hand, at SV=7200 hr -1 , although the removal rate is lower than that of SV=1200 hr -1 , it is assumed that water containing 6.0 μg/L of TPN is filtered at a flow rate of 1.8 liter/min for 1 day. In the case of 15 liters, more than 50% of TNP can be removed using a fixed type water purifier-B for about 7 months.

又，根據二氯松(DDVP)之除去率測定結果，於SV=1200小時-1 下，實施例7之濾材與比較例7之活性碳相比較高地維持除去率，直至通水約32小時為止除去率為80%以上。認為上述情況係由於DDVP之分子量稍大為221，故而吸附速度較快之實施例7之濾材與比較例7之活性碳相比較為有利。再者，由於DDVP對水之溶解度非常大為10克/升，故而平衡吸附量較小，因此，通水約32小時之前除去率為80%以上，但其後除去率降低，於通水約43小時下除去率為50%。再者，通水約32小時相當於使用固定型淨水器-A且假設將含有6.0微克/升之DDVP之水以3.0升/分鐘之流速1天過濾25升之情形時使用約8個月，通水約43小時相當於使用約10個月。Further, according to the measurement result of the removal rate of diclofen (DDVP), the filter material of Example 7 maintained the removal rate higher than that of the activated carbon of Comparative Example 7 at SV = 1,200 hr -1 until the water was passed for about 32 hours. The removal rate was 80% or more. The above case is considered to be because the molecular weight of DDVP is slightly larger than 221, so that the filter material of Example 7 having a faster adsorption speed is more advantageous than the activated carbon of Comparative Example 7. Furthermore, since the solubility of DDVP to water is very large at 10 g/liter, the equilibrium adsorption amount is small. Therefore, the removal rate is more than 80% before the passage of water for about 32 hours, but the removal rate thereafter decreases. The removal rate was 50% at 43 hours. Furthermore, the passage of water for about 32 hours is equivalent to the use of the fixed type water purifier-A and it is assumed that the water containing 6.0 μg/L of DDVP is filtered for 25 liters per day for a period of about 8 months. It takes about 43 hours to pass the water for about 10 months.

又，根據溶解性鉛之除去率測定結果，於SV=1200小時-1 下，實施例7之濾材與比較例7之活性碳相比維持較高之除去率，於通水約22小時下除去率為50%以上。再者，比較例7之活性碳係於通水約8小時下除去率便為50%以下。認為上述情況表示實施例7之濾材中存在較多容易吸附鉛之活性點。而且，根據試驗之結果推定為：於使用固定型淨水器-A且假設將含有6微克/升(以鉛換算)之溶解性鉛之水以3.0升/分鐘之流速1天過濾25升之情形時，約5個月可將50%以上之鉛除去。Further, according to the results of the solubility of lead is removed for determination of at SV = 1200 hr -1, the activated carbon filter of Comparative Example 7 Example 7 of the comparison to maintain a high removal rate of removing the water for about 22 hours to pass The rate is 50% or more. Further, in the activated carbon of Comparative Example 7, the removal rate was 50% or less in about 8 hours. It is considered that the above indicates that there are many active sites in the filter medium of Example 7 which are likely to adsorb lead. Further, based on the results of the test, it is presumed that the fixed type water purifier-A is used and it is assumed that 6 μg/L (in terms of lead) of soluble lead water is filtered at a flow rate of 3.0 liter/min for 25 days. In the case, more than 50% of the lead can be removed in about 5 months.

又，根據游離氯之除去率測定結果，於SV=1200小時-1 下，實施例7之濾材與比較例7相比較高地維持除去率，於通水48小時後亦為約80%。根據游離氯係藉由在濾材表面之還原反應而除去推定為，實施例7之濾材不僅粒內擴散速度較快，而且於表面容易還原游離氯之活性點較多。而且，根據試驗之結果推定為：於使用固定型淨水器-A且假設將含有0.2毫克/升(氯換算)之游離氯之水以3.0升/分鐘之流速1天過濾25升之情形時，約1年可將80%以上之游離氯除去。另一方面，於SV=7200小時-1 下，在通水48小時後亦為約60%之除去率。而且，根據試驗之結果推定為於使用固定型淨水器-B且假設將含有2.0毫克/升(氯換算)之游離氯之水以1.8升/分鐘之流速1天過濾15升之情形時，約1年可將60%以上之游離氯除去。Further, based on the measurement result of the removal rate of free chlorine, the filter material of Example 7 maintained a higher removal rate than that of Comparative Example 7 at SV = 1,200 hr -1 , and was also about 80% after 48 hours of water passing. According to the removal of the free chlorine by the reduction reaction on the surface of the filter medium, it is estimated that the filter material of the seventh embodiment has a high diffusion rate in the particles and a large number of active sites for easily reducing free chlorine on the surface. Further, based on the results of the test, it is presumed that when the fixed type water purifier-A is used and it is assumed that water containing 0.2 mg/liter (in terms of chlorine) of free chlorine is filtered at a flow rate of 3.0 liter/min for 25 days, 25 liters is filtered. More than 80% of free chlorine can be removed in about 1 year. On the other hand, at SV = 7,200 hr -1 , the removal rate was also about 60% after 48 hours of water passing. Further, according to the results of the test, it is presumed that when the fixed type water purifier-B is used and it is assumed that water containing 2.0 mg/liter (in terms of chlorine) of free chlorine is filtered at a flow rate of 1.8 liter/min for 15 days, 15 liters is filtered. More than 60% of the free chlorine can be removed in about 1 year.

又，根據總有機鹵素(包括自腐植質產生之有機鹵化合物)之除去率測定結果，於SV=1200小時-1 下，直至通水48 小時為止，實施例7之濾材之除去率較比較例7之活性碳高。再者，認為由於TOX成分中包含分子量較大之物質，故而吸附速度較快之實施例7之濾材之除去率較比較例7之活性碳大。而且，根據試驗之結果推定為於使用固定型淨水器-A且假設將含有TOX濃度為130微克(氯換算)/升之總有機鹵素之水以3.0升/分鐘之流速1天過濾25升之情形時，約4個月可除去50%以上。Further, according to the measurement result of the removal rate of the total organic halogen (including the organic halogen compound produced from the humus), the removal rate of the filter medium of Example 7 was compared with the comparative example at SV = 1,200 hr -1 until the water was passed for 48 hours. 7 has a high activated carbon. Further, it is considered that since the TOX component contains a substance having a large molecular weight, the removal rate of the filter medium of Example 7 which is faster in adsorption speed is larger than that of Comparative Example 7. Further, according to the results of the test, it is presumed that the fixed type water purifier-A is used and it is assumed that water containing a total organic halogen having a TOX concentration of 130 μg (in terms of chlorine) per liter is filtered at a flow rate of 3.0 liter/min for 25 days. In the case of the situation, more than 50% can be removed in about 4 months.

[實施例8][Embodiment 8]

實施例8為實施例1~實施例7之變形。於實施例8中，如圖18(A)所示之模式性局部剖面圖般，將實施例1~實施例7中說明之濾材組入帶有帽部件30之瓶(所謂寶特瓶)20中。具體而言，於帽部件30之內部配置實施例1~實施例7之濾材40，且以濾材40不流出之方式於帽部件30之液體流入側及液體排出側配置過濾器31、32。繼而，藉由使瓶20內之液體或水(飲用水或化妝水等)21通過配置於帽部件30之內部之濾材40而飲用或使用，可增加例如液體(水)中之礦物成分。再者，帽部件30通常使用未圖示之蓋予以封閉。Embodiment 8 is a modification of Embodiments 1 to 7. In the eighth embodiment, the filter materials described in the first to seventh embodiments are assembled into the bottle with the cap member 30 (so-called bottle) 20 as shown in the schematic partial cross-sectional view shown in Fig. 18(A). in. Specifically, the filter materials 40 of the first to seventh embodiments are disposed inside the cap member 30, and the filters 31 and 32 are disposed on the liquid inflow side and the liquid discharge side of the cap member 30 so that the filter medium 40 does not flow out. Then, by drinking or using the liquid or water (drinking water or lotion, etc.) 21 in the bottle 20 through the filter medium 40 disposed inside the cap member 30, for example, the mineral component in the liquid (water) can be increased. Furthermore, the cap member 30 is usually closed by a cover (not shown).

或者，如圖18(B)所示之模式性剖面圖般，亦可採用於具有透水性之袋50中儲存實施例1~實施例7之濾材40，並將該袋50投入至瓶20內之液體或水(飲用水或化妝水等)21中之形態。再者，參照編號22為用以封閉瓶20之口部之帽。或者，如圖19(A)所示之模式性剖面圖般，於吸管部件60之內部配置實施例1~實施例7之濾材40，且以濾材40不流出之方式於吸管部件之液體流入側及液體排出側配置 未圖示之過濾器。繼而，藉由使瓶20內之液體或水(飲用水)21通過配置於吸管部件60之內部之實施例1~實施例7之濾材40而飲用，可增加液體(水)中之礦物成分。或者，如圖19(B)所示之局部切缺之模式面般，於噴霧部件70之內部配置實施例1~實施例7之濾材40，且以濾材40不流出之方式於噴霧部件70之液體流入側及液體排出側配置未圖示之過濾器。繼而，藉由按壓設置於噴霧部件70之按鈕71，使瓶20內之液體或水(飲用水或化妝水等)21通過配置於噴霧部件70之內部之實施例1~實施例7之濾材40，自噴霧孔72噴霧，可增加液體(水)中之礦物成分。Alternatively, as shown in the schematic cross-sectional view shown in FIG. 18(B), the filter medium 40 of Examples 1 to 7 may be stored in the water-permeable bag 50, and the bag 50 may be put into the bottle 20. The form of liquid or water (drinking water or lotion, etc.) 21. Further, reference numeral 22 is a cap for closing the mouth of the bottle 20. Alternatively, as shown in the schematic cross-sectional view shown in Fig. 19(A), the filter medium 40 of the first to seventh embodiments is placed inside the straw member 60, and the liquid material inflow side of the straw member is not flowed out. And liquid discharge side configuration Filter not shown. Then, by allowing the liquid or water (drinking water) 21 in the bottle 20 to be drunk by the filter materials 40 of the first to seventh embodiments disposed inside the straw member 60, the mineral component in the liquid (water) can be increased. Alternatively, as shown in FIG. 19(B), the filter material 40 of the first to seventh embodiments is disposed inside the spray member 70, and the filter member 40 is not discharged out of the spray member 70. A filter (not shown) is disposed on the liquid inflow side and the liquid discharge side. Then, by pressing the button 71 provided on the spray member 70, the liquid or water (drinking water or lotion, etc.) 21 in the bottle 20 is passed through the filter medium 40 of the first to seventh embodiments disposed inside the spray member 70. Spraying from the spray hole 72 can increase the mineral content in the liquid (water).

以上，基於較佳實施例對本發明進行了說明，但本發明並不限定於該等實施例，可進行各種變形。作為濾材，可設為組合有實施例1中所說明之濾材與陶瓷製之濾材(具有微細之孔之陶瓷製之濾材)之淨水器、組合有實施例1中所說明之濾材與離子交換樹脂之淨水器。又，亦可對構成本發明之濾材之多孔質碳材料進行造粒而使用。The present invention has been described above based on the preferred embodiments, but the present invention is not limited to the embodiments, and various modifications can be made. The filter medium may be a water purifier in which the filter medium described in the first embodiment and a filter medium made of ceramics (ceramic filter material having fine pores) are combined, and the filter medium and ion exchange described in the first embodiment are combined. Resin water purifier. Further, the porous carbon material constituting the filter medium of the present invention may be granulated and used.

於實施例中，對使用稻殼作為多孔質碳材料之原料之情形進行了說明，但亦可使用其他植物作為原料。此處，作為其他植物，例如可列舉稻桿、蘆葦或裙帶菜梗絲、植生於陸地上之維管束植物、蕨類植物、苔蘚植物、藻類及海草等，該等可單獨使用，亦可混合複數種而使用。具體而言，例如可將作為多孔質碳材料之原料的源自植物之材料設為稻之稻桿(例如鹿兒島產：無農藥米(isehikari))，藉由將作為原料之稻桿碳化使其轉換為碳質物質(多孔質碳材 料前驅物)，其次實施酸處理而獲得多孔質碳材料。或者，將作為多孔質碳材料之原料的源自植物之材料設為稻科之蘆葦，藉由將作為原料之稻科之蘆葦碳化使其轉換為碳質物質(多孔質碳材料前驅物)，其次實施酸處理而獲得多孔質碳材料。又，以氫氧化鈉水溶液等鹼(鹼基)代替氫氟酸水溶液進行處理所得之多孔質碳材料亦可獲得相同之結果。In the examples, the case where the rice husk is used as the raw material of the porous carbon material has been described, but other plants may be used as the raw material. Here, as other plants, for example, rice straw, reed or wakame stem, vascular plants planted on land, ferns, bryophytes, algae, and seaweed may be mentioned, and these may be used alone or in combination. Use in multiples. Specifically, for example, a plant-derived material which is a raw material of a porous carbon material can be used as a rice straw (for example, Kagoshima: isehikari), and carbonized rice straw as a raw material can be used. Converted to carbonaceous material (porous carbon material) The material precursor was subjected to an acid treatment to obtain a porous carbon material. Alternatively, the plant-derived material which is a raw material of the porous carbon material is a reed of the genus Polygonaceae, and is converted into a carbonaceous substance (porous carbon material precursor) by carbonizing the reeds of the rice family as a raw material. Next, an acid treatment is carried out to obtain a porous carbon material. Further, the same results can be obtained by a porous carbon material obtained by treating a base (base) such as an aqueous sodium hydroxide solution instead of a hydrofluoric acid aqueous solution.

或者，將作為多孔質碳材料之原料的源自植物之材料設為裙帶菜梗絲(岩手縣三陸產)，藉由將作為原料之裙帶菜梗絲碳化使其轉換為碳質物質(多孔質碳材料前驅物)，其次實施酸處理而獲得多孔質碳材料。具體而言，首先例如將裙帶菜梗絲於500℃左右之溫度下加熱、碳化。再者，於加熱前，例如亦可以醇對成為原料之裙帶菜梗絲進行處理。作為具體之處理方法，可列舉浸漬於乙醇等中之方法，藉此，可減少原料中所含之水分，並且可使最終所獲得之多孔質碳材料中所含之除碳以外之其他元素、或礦物成分溶出。又，可藉由上述利用醇之處理，而抑制碳化時之氣體之產生。更具體而言，使裙帶菜梗絲於乙醇中浸漬48小時。再者，較佳為於乙醇中實施超音波處理。其次，藉由將該裙帶菜梗絲於氮氣流中於500℃下加熱5小時使其碳化，而獲得碳化物。再者，藉由進行此種處理(預碳化處理)，可減少或除去後續之碳化時可能生成之焦油成分。其後，將10克該碳化物加入至氧化鋁製之坩堝中，於氮氣流中(10升/分鐘)以5℃/分鐘之升溫速度升溫至 1000℃。繼而，於1000℃下碳化5小時使其轉換為碳質物質(多孔質碳材料前驅物)後冷卻至室溫。再者，於碳化及冷卻中使氮氣持續流通。其次，藉由使該多孔質碳材料前驅物於46容積%之氫氟酸水溶液浸漬一晚而進行酸處理後，使用水及乙醇清洗至pH值成為7。繼而，最後進行乾燥，藉此可獲得多孔質碳材料。Alternatively, the plant-derived material which is a raw material of the porous carbon material is a wakame stalk (Iwate Sanlu), which is converted into a carbonaceous substance by carbonizing the wakame stem as a raw material. The carbon material precursor) is subjected to an acid treatment to obtain a porous carbon material. Specifically, first, for example, the wakame stem is heated and carbonized at a temperature of about 500 °C. Further, before heating, for example, the wakame stem yarn which becomes a raw material may be treated with alcohol. As a specific treatment method, a method of immersing in ethanol or the like can be used, whereby the moisture contained in the raw material can be reduced, and other elements other than carbon contained in the finally obtained porous carbon material can be Or mineral components are dissolved. Further, the above-described treatment with an alcohol can suppress the generation of gas at the time of carbonization. More specifically, the wakame stem was immersed in ethanol for 48 hours. Further, it is preferred to carry out ultrasonic treatment in ethanol. Next, carbides were obtained by heating the wakame stems in a nitrogen stream at 500 ° C for 5 hours to carbonize them. Further, by performing such a treatment (pre-carbonization treatment), it is possible to reduce or remove the tar component which may be generated upon subsequent carbonization. Thereafter, 10 g of this carbide was added to a crucible made of alumina, and the temperature was raised to a temperature increase rate of 5 ° C / min in a nitrogen stream (10 l / min) to 1000 ° C. Then, it was carbonized at 1000 ° C for 5 hours to be converted into a carbonaceous substance (porous carbon material precursor), and then cooled to room temperature. Further, nitrogen gas is continuously circulated during carbonization and cooling. Next, the porous carbon material precursor was subjected to an acid treatment by immersing it in a 46% by volume hydrofluoric acid aqueous solution overnight, and then washed with water and ethanol until the pH became 7. Then, drying is finally performed, whereby a porous carbon material can be obtained.

1‧‧‧碳/聚合物複合體1‧‧‧Carbon/Polymer Complex

2‧‧‧不織布2‧‧‧nonwoven

10‧‧‧淨水器本體10‧‧‧Water purifier body

11‧‧‧多孔質碳材料11‧‧‧Porous carbon material

12‧‧‧第1填充部12‧‧‧1st filling section

13‧‧‧棉13‧‧‧ cotton

14‧‧‧第2填充部14‧‧‧2nd filling section

15‧‧‧流入口15‧‧‧Inlet

16‧‧‧流出口16‧‧‧Exit

20‧‧‧瓶20‧‧‧ bottles

21‧‧‧液體或水21‧‧‧Liquid or water

22‧‧‧帽22‧‧‧ Cap

30‧‧‧帽部件30‧‧‧Cap parts

31、32‧‧‧過濾器31, 32‧‧‧ filter

40‧‧‧濾材40‧‧‧ Filter media

50‧‧‧袋50‧‧‧ bags

60‧‧‧吸管部件60‧‧‧Sipper parts

70‧‧‧噴霧部件70‧‧‧Spray parts

71‧‧‧按鈕71‧‧‧ button

72‧‧‧噴霧孔72‧‧‧ spray hole

圖1(A)及(B)係分別表示實施例1A之濾材、比較例1A及比較例1B之濾材之試驗時間與每1克濾材之亞甲基藍及黑5吸附量之關係之圖表。1(A) and (B) are graphs showing the relationship between the test time of the filter medium of Example 1A, the filter materials of Comparative Example 1A and Comparative Example 1B, and the adsorption amount of methylene blue and black 5 per gram of the filter medium, respectively.

圖2係表示將實施例1B、參考例1、比較例1C及比較例1D之試樣分別填充至濾筒中，並使亞甲基藍水溶液流入濾筒內，測定自濾筒流出之水之亞甲基藍濃度所得之結果之圖表。2 is a view showing that the samples of Example 1B, Reference Example 1, Comparative Example 1C, and Comparative Example 1D were each filled in a filter cartridge, and a methylene blue aqueous solution was flowed into the filter cartridge to measure the concentration of methylene blue in the water flowing out of the cartridge. Chart of results.

圖3係實施例1之淨水器之模式性剖面圖。Figure 3 is a schematic cross-sectional view of the water purifier of Example 1.

圖4係表示實施例1之污染物質除去板片部件之模式性剖面構造之圖。Fig. 4 is a view showing a schematic cross-sectional structure of the pollutant removing sheet member of the first embodiment.

圖5係表示實施例2之包含多孔質碳材料之濾材、比較例2A、比較例2B、比較例2C之濾材的氯除去率之圖表。Fig. 5 is a graph showing the chlorine removal rate of the filter medium containing the porous carbon material of Example 2, the filter materials of Comparative Example 2A, Comparative Example 2B, and Comparative Example 2C.

圖6(A)、(B)及(C)係分別表示實施例3之包含多孔質碳材料之濾材及比較例3之濾材中的氯、1,1,1-三氯乙烷、CAT之除去率之圖表。6(A), (B) and (C) show chlorine, 1,1,1-trichloroethane and CAT in the filter medium containing the porous carbon material of Example 3 and the filter medium of Comparative Example 3, respectively. A chart of removal rates.

圖7係表示實施例4之包含多孔質碳材料之濾材及比較例4之濾材中的微囊藻毒素LR之除去率之圖表。Fig. 7 is a graph showing the removal rate of microcystins LR in the filter medium containing the porous carbon material of Example 4 and the filter medium of Comparative Example 4.

圖8係表示實施例5之包含多孔質碳材料之濾材及比較例5之濾材的高速吸附特性及粒徑依存性之圖表。Fig. 8 is a graph showing the high-speed adsorption characteristics and particle diameter dependence of the filter medium containing the porous carbon material of Example 5 and the filter material of Comparative Example 5.

圖9(A)~(D)係分別表示實施例6a、實施例6a'、實施例6b、實施例6b'、實施例6c、實施例6c'、實施例6d及實施例6d'之試樣之X射線繞射結果之圖表。9(A) to (D) show samples of Example 6a, Example 6a', Example 6b, Example 6b', Example 6c, Example 6c', Example 6d, and Example 6d', respectively. A chart of the X-ray diffraction results.

圖10(A)及(B)係表示實施例6A、實施例6B、實施例6C及實施例6D之濾材、以及比較例6之孔隙容積之測定結果之圖表。10(A) and (B) are graphs showing measurement results of the pore volume of the filter materials of Examples 6A, 6B, 6C and 6D and Comparative Example 6.

圖11係表示實施例6A、實施例6B、實施例6C及實施例6D之濾材、以及比較例6之藉由非定域化密度泛函數法求出之孔隙徑分佈之測定結果之圖表。Fig. 11 is a graph showing the measurement results of the pore diameter distributions obtained by the non-localized density functional method of the filter materials of Example 6A, Example 6B, Example 6C, and Example 6D, and Comparative Example 6.

圖12(A)及(B)係表示實施例7及比較例7之試樣之十二烷基苯磺酸鈉之除去率測定結果之圖表。Fig. 12 (A) and (B) are graphs showing the results of measurement of the removal rate of sodium dodecylbenzenesulfonate in the samples of Example 7 and Comparative Example 7.

圖13(A)及(B)係表示實施例7及比較例7之試樣之百菌清之除去率測定結果之圖表。Fig. 13 (A) and (B) are graphs showing the results of measurement of the removal rate of chlorothalonil in the samples of Example 7 and Comparative Example 7.

圖14係表示實施例7及比較例7之試樣之二氯松之除去率測定結果之圖表。Fig. 14 is a graph showing the results of measurement of the removal rate of diclosan of the samples of Example 7 and Comparative Example 7.

圖15係表示實施例7及比較例7之試樣之溶解性鉛之除去率測定結果之圖表。Fig. 15 is a graph showing the results of measurement of the removal rate of soluble lead in the samples of Example 7 and Comparative Example 7.

圖16(A)及(B)係表示實施例7及比較例7之試樣之游離氯之除去率測定結果之圖表。16(A) and 16(B) are graphs showing the results of measurement of the removal rate of free chlorine in the samples of Example 7 and Comparative Example 7.

圖17係表示實施例7及比較例7之試樣之總有機鹵素之除去率測定結果之圖表。Fig. 17 is a graph showing the results of measurement of the removal rate of total organic halogen in the samples of Example 7 and Comparative Example 7.

圖18(A)及(B)係實施例8之瓶之模式性局部剖面圖及模 式性剖面圖。18(A) and (B) are schematic partial cross-sectional views and models of the bottle of Example 8. Profile view.

圖19(A)及(B)係實施例8之瓶之變形例之模式性局部剖面圖及局部切缺之模式面。19(A) and (B) are schematic partial cross-sectional views and a partial cut-out mode surface of a modified example of the bottle of the eighth embodiment.

Claims (30)

一種污染物質除去劑，其包含如下多孔質碳材料：藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，藉由BJH法所得之孔隙之容積為0.3cm3 /克以上，且粒徑為75μm以上。A pollutant removing agent comprising a porous carbon material having a specific surface area obtained by a nitrogen BET method of 1 × 10 2 m 2 /g or more, and a volume of pores obtained by a BJH method of 0.3 cm 3 / More than gram, and the particle size is 75 μm or more. 一種污染物質除去劑，其包含如下多孔質碳材料：藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，藉由非定域化密度泛函數法求出之直徑為1×10-9 m至5×10-7 m之孔隙之容積之合計為1.0cm3 /克以上，且粒徑為75μm以上。A pollutant removing agent comprising a porous carbon material having a specific surface area obtained by a nitrogen BET method of 1 × 10 2 m 2 /g or more, which is obtained by a delocalized density functional method The total volume of the pores having a diameter of from 1 × 10 -9 m to 5 × 10 -7 m is 1.0 cm 3 /g or more, and the particle diameter is 75 μm or more. 一種污染物質除去劑，其包含如下多孔質碳材料：藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，於藉由非定域化密度泛函數法求出之孔隙徑分佈中在3nm至20nm之範圍內具有至少1個峰值，具有於3nm至20nm之範圍內之孔隙徑之孔隙之容積之合計所占之比率為所有孔隙之容積總計之0.2以上，且粒徑為75μm以上。A pollutant removing agent comprising a porous carbon material obtained by a nitrogen BET method having a specific surface area of 1 × 10 2 m 2 /g or more, which is obtained by a delocalized density functional method The pore diameter distribution has at least one peak in the range of 3 nm to 20 nm, and the ratio of the volume of the pores having the pore diameter in the range of 3 nm to 20 nm accounts for 0.2 or more of the total volume of all the pores, and The particle diameter is 75 μm or more. 一種污染物質除去劑，其包含如下多孔質碳材料：藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，藉由汞滲法所得之孔隙之容積為1.0cm3 /克以上，且粒徑為75μm以上。A pollutant removing agent comprising a porous carbon material having a specific surface area obtained by a nitrogen BET method of 1 × 10 2 m 2 /g or more, and a volume of pores obtained by a mercury infiltration method of 1.0 cm 3 / gram or more, and the particle diameter is 75 μm or more. 如請求項1至4中任一項之污染物質除去劑，其中多孔質碳材料之鬆密度為0.1克/cm3 至0.8克/cm3 。The pollutant removing agent according to any one of claims 1 to 4, wherein the porous carbon material has a bulk density of from 0.1 g/cm 3 to 0.8 g/cm 3 . 一種碳/聚合物複合體，其係除去污染物質且包含多孔質碳材料及黏合劑，上述多孔質碳材料係藉由氮BET法所 得之比表面積之值為1×102 m2 /克以上，藉由BJH法所得之孔隙之容積為0.3cm3 /克以上，且粒徑為75μm以上。A carbon/polymer composite which removes a pollutant and comprises a porous carbon material and a binder, and the porous carbon material has a specific surface area obtained by a nitrogen BET method of 1 × 10 2 m 2 /g or more. The volume of the pores obtained by the BJH method is 0.3 cm 3 /g or more, and the particle diameter is 75 μm or more. 一種碳/聚合物複合體，其係除去污染物質且包含多孔質碳材料及黏合劑，上述多孔質碳材料係藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，藉由非定域化密度泛函數法求出之直徑為1×10-9 m至5×10-7 m之孔隙之容積之合計為1.0cm3 /克以上，且粒徑為75μm以上。A carbon/polymer composite which removes a pollutant and comprises a porous carbon material and a binder, and the porous carbon material has a specific surface area obtained by a nitrogen BET method of 1 × 10 2 m 2 /g or more. , determined by the diameter of delocalized density functional method of the total volume of -9 m to 5 × 10 -7 m of pores of not less than 1 × 10 1.0cm 3 / g, and a particle diameter of 75μm or more . 一種碳/聚合物複合體，其係除去污染物質且包含多孔質碳材料及黏合劑，上述多孔質碳材料係藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，於藉由非定域化密度泛函數法求出之孔隙徑分佈中在3nm至20nm之範圍內具有至少1個峰值，具有於3nm至20nm之範圍內之孔隙徑之孔隙之容積之合計所占之比率為所有孔隙之容積總計之0.2以上，且粒徑為75μm以上。A carbon/polymer composite which removes a pollutant and comprises a porous carbon material and a binder, and the porous carbon material has a specific surface area obtained by a nitrogen BET method of 1 × 10 2 m 2 /g or more. The total volume of the pores having a pore diameter in the range of 3 nm to 20 nm in the range of 3 nm to 20 nm in the pore diameter distribution determined by the delocalized density-Fan function method The ratio is a total of 0.2 or more of the total volume of all the pores, and the particle diameter is 75 μm or more. 一種碳/聚合物複合體，其係除去污染物質且包含多孔質碳材料及黏合劑，上述多孔質碳材料係藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，藉由汞滲法所得之孔隙之容積為1.0cm3 /克以上，且粒徑為75μm以上。A carbon/polymer composite which removes a pollutant and comprises a porous carbon material and a binder, and the porous carbon material has a specific surface area obtained by a nitrogen BET method of 1 × 10 2 m 2 /g or more. The volume of the pores obtained by the mercury infiltration method is 1.0 cm 3 /g or more, and the particle diameter is 75 μm or more. 一種污染物質除去板片部件，其包含多孔質碳材料及支持部件，上述多孔質碳材料係藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，藉由BJH法所得之孔隙之容積為0.3cm3 /克以上，且粒徑為75μm以上。A pollutant removing sheet member comprising a porous carbon material and a supporting member, wherein the porous carbon material has a specific surface area obtained by a nitrogen BET method of 1 × 10 2 m 2 /g or more, by a BJH method The volume of the obtained pores was 0.3 cm 3 /g or more, and the particle diameter was 75 μm or more. 一種污染物質除去板片部件，其包含多孔質碳材料及支持部件，上述多孔質碳材料係藉由氮BET法所得之比表 面積之值為1×102 m2 /克以上，藉由非定域化密度泛函數法求出之直徑為1×10-9 m至5×10-7 m之孔隙之容積之合計為1.0cm3 /克以上，且粒徑為75μm以上。A pollutant removing sheet member comprising a porous carbon material and a supporting member, wherein the porous carbon material has a specific surface area obtained by a nitrogen BET method of 1 × 10 2 m 2 /g or more, by The volume of the pores having a diameter of from 1 × 10 -9 m to 5 × 10 -7 m, which is obtained by the domain density density function method, is 1.0 cm 3 /g or more in total, and the particle diameter is 75 μm or more. 一種污染物質除去板片部件，其包含多孔質碳材料及支持部件，上述多孔質碳材料係藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，於藉由非定域化密度泛函數法求出之孔隙徑分佈中在3nm至20nm之範圍內具有至少1個峰值，具有於3nm至20nm之範圍內之孔隙徑之孔隙之容積之合計所占之比率為所有孔隙之容積總計之0.2以上，且粒徑為75μm以上。A pollutant removing sheet member comprising a porous carbon material and a supporting member, wherein the porous carbon material has a specific surface area obtained by a nitrogen BET method of 1 × 10 2 m 2 /g or more; The ratio of the volume of the pore diameter distribution in the range of 3 nm to 20 nm in the pore diameter distribution determined by the localized density function method is the ratio of the volume of the pores having the pore diameter in the range of 3 nm to 20 nm. The volume of all the pores is 0.2 or more in total, and the particle diameter is 75 μm or more. 一種污染物質除去板片部件，其包含多孔質碳材料及支持部件，上述多孔質碳材料係藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，藉由汞滲法所得之孔隙之容積為1.0cm3 /克以上，且粒徑為75μm以上。A pollutant removing sheet member comprising a porous carbon material and a supporting member, wherein the porous carbon material has a specific surface area obtained by a nitrogen BET method of 1 × 10 2 m 2 /g or more, by mercury infiltration The volume of the pores obtained by the method is 1.0 cm 3 /g or more, and the particle diameter is 75 μm or more. 一種濾材，其包含如下多孔質碳材料：藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，藉由BJH法所得之孔隙之容積為0.3cm3 /克以上，且粒徑為75μm以上。A filter material comprising a porous carbon material having a specific surface area obtained by a nitrogen BET method of 1 × 10 2 m 2 /g or more, and a volume of pores obtained by a BJH method of 0.3 cm 3 /g or more, And the particle size is 75 μm or more. 如請求項14之濾材，其中多孔質碳材料之鬆密度為0.1克/cm3 至0.8克/cm3 。The filter material of claim 14, wherein the porous carbon material has a bulk density of from 0.1 g/cm 3 to 0.8 g/cm 3 . 一種濾材，其包含如下多孔質碳材料：藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，藉由非定域化密度泛函數法求出之直徑為1×10-9 m至5×10-7 m之孔隙之容積之合計為1.0cm3 /克以上，且粒徑為75μm以上。A filter material comprising a porous carbon material having a specific surface area obtained by a nitrogen BET method of 1 × 10 2 m 2 /g or more, and having a diameter of 1 by a delocalized density functional method The total volume of the pores of ×10 -9 m to 5 × 10 -7 m is 1.0 cm 3 /g or more, and the particle diameter is 75 μm or more. 一種濾材，其包含如下多孔質碳材料：藉由氮BET法所 得之比表面積之值為1×102 m2 /克以上，於藉由非定域化密度泛函數法求出之孔隙徑分佈中在3nm至20nm之範圍內具有至少1個峰值，具有於3nm至20nm之範圍內之孔隙徑之孔隙之容積之合計所占之比率為所有孔隙之容積總計之0.2以上，且粒徑為75μm以上。A filter material comprising the following porous carbon material: a specific surface area obtained by a nitrogen BET method having a value of 1×10 2 m 2 /g or more, and a pore diameter determined by a delocalized density functional method The distribution has at least one peak in the range of 3 nm to 20 nm, and the ratio of the volume of the pores having the pore diameter in the range of 3 nm to 20 nm accounts for 0.2 or more of the total volume of all the pores, and the particle diameter is 75 μm or more. 一種濾材，其包含如下多孔質碳材料：藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，藉由汞滲法所得之孔隙之容積為1.0cm3 /克以上，且粒徑為75μm以上。A filter material comprising a porous carbon material having a specific surface area obtained by a nitrogen BET method of 1 × 10 2 m 2 /g or more, and a volume of pores obtained by a mercury infiltration method of 1.0 cm 3 /g or more And the particle size is 75 μm or more. 一種濾材，其包含如下多孔質碳材料：藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，藉由BJH法所得之孔隙之容積為0.1cm3 /克以上，且以含有鈉成分之植物為原料。A filter material comprising a porous carbon material having a specific surface area obtained by a nitrogen BET method of 1 × 10 2 m 2 /g or more, and a volume of pores obtained by a BJH method of 0.1 cm 3 /g or more, The plant containing the sodium component is used as a raw material. 一種濾材，其包含如下多孔質碳材料：藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，藉由非定域化密度泛函數法求出之直徑為1×10-9 m至5×10-7 m之孔隙之容積之合計為0.1cm3 /克以上，且以含有選自由鈉、鎂、鉀及鈣所組成之群中之至少1種成分之植物為原料。A filter material comprising a porous carbon material having a specific surface area obtained by a nitrogen BET method of 1 × 10 2 m 2 /g or more, and having a diameter of 1 by a delocalized density functional method The total volume of the pores of ×10 -9 m to 5 × 10 -7 m is 0.1 cm 3 /g or more, and the plant containing at least one component selected from the group consisting of sodium, magnesium, potassium, and calcium As raw materials. 一種濾材，其包含如下多孔質碳材料：藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，於藉由非定域化密度泛函數法求出之孔隙徑分佈中在3nm至20nm之範圍內具有至少1個峰值，具有於3nm至20nm之範圍內之孔隙徑之孔隙之容積之合計所占之比率為所有孔隙之容積總計之0.1以上，且以含有選自由鈉、鎂、鉀及鈣所組成之群中之至少1種成分之植物為原料。A filter material comprising the following porous carbon material: a specific surface area obtained by a nitrogen BET method having a value of 1×10 2 m 2 /g or more, and a pore diameter determined by a delocalized density functional method The distribution has at least one peak in the range of 3 nm to 20 nm, and the ratio of the volume of the pores having the pore diameter in the range of 3 nm to 20 nm accounts for 0.1 or more of the total volume of all the pores, and contains A plant containing at least one of a group consisting of free sodium, magnesium, potassium, and calcium is used as a raw material. 一種濾材，其包含如下多孔質碳材料：藉由氮BET法所得之比表面積之值為1×102 m2 /克以上，藉由汞滲法所得之孔隙之容積為1.0cm3 /克以上，且以含有選自由鈉、鎂、鉀及鈣所組成之群中之至少1種成分之植物為原料。A filter material comprising a porous carbon material having a specific surface area obtained by a nitrogen BET method of 1 × 10 2 m 2 /g or more, and a volume of pores obtained by a mercury infiltration method of 1.0 cm 3 /g or more And a plant containing at least one component selected from the group consisting of sodium, magnesium, potassium, and calcium is used as a raw material. 如請求項19至22中任一項之濾材，其中向硬度為0.1以下之水50毫升中添加1克濾材，經過6小時後之硬度為5以上。 The filter medium according to any one of claims 19 to 22, wherein 1 g of the filter medium is added to 50 ml of water having a hardness of 0.1 or less, and the hardness after 5 hours is 5 or more. 一種濾材，其包含如請求項14至17中任一項之多孔質碳材料，於將含有1微克/升之分子量為1×102 至1×105 之物質之水於空間速度1200小時-1 下連續進行48小時通液時，直至該物質之除去率達到80%為止之時間為使用椰殼活性碳時之直至該物質之除去率達到80%為止之時間的2倍以上。A filter material comprising the porous carbon material according to any one of claims 14 to 17, wherein the water having a molecular weight of 1 × 10 2 to 1 × 10 5 having a molecular weight of 1 μg / liter is at a space velocity of 1200 hours - continuously for 48 hours at a liquid flow, until the rate of removal of material until the time to reach 80% of the removal rate of the material until the time of use coconut shell activated carbon more than two times the time until 80%. 一種濾材，其包含如請求項14至17中任一項之多孔質碳材料，於將含有0.9毫克/升十二烷基苯磺酸鹽之水於空間速度1200小時-1 下連續進行25小時通液時，十二烷基苯磺酸鹽之除去率為10%以上。A filter material comprising the porous carbon material according to any one of claims 14 to 17, wherein the water containing 0.9 mg/liter of dodecylbenzenesulfonate is continuously subjected to a space velocity of 1200 hours -1 for 25 hours. When the liquid was passed through, the removal rate of dodecylbenzenesulfonate was 10% or more. 一種濾材，其包含如請求項14至17中任一項之多孔質碳材料，於將含有6微克/升百菌清之水於空間速度1200小時-1 下連續進行50小時通液時，百菌清之除去率為60%以 上。A filter material comprising the porous carbon material according to any one of claims 14 to 17, when the water containing 6 μg/liter of chlorothalonil is continuously passed for 50 hours at a space velocity of 1200 hours -1 , The removal rate of the bacterial clear is 60% or more. 一種濾材，其包含如請求項14至17中任一項之多孔質碳材料，於將含有6微克/升二氯松之水於空間速度1200小時-1 下連續進行25小時通液時，二氯松之除去率為60%以上。A filter material comprising the porous carbon material according to any one of claims 14 to 17, wherein the water containing 6 μg/L of diclofen is continuously passed for 25 hours at a space velocity of 1200 hours -1 , The removal rate of the pine is 60% or more. 一種濾材，其包含如請求項14至17中任一項之多孔質碳材料，於將含有6微克/升溶解性鉛之水於空間速度1200小時-1 下連續進行25小時通液時，溶解性鉛之除去率為30%以上。A filter material comprising the porous carbon material according to any one of claims 14 to 17, which is dissolved when water containing 6 μg/L of soluble lead is continuously passed for 25 hours at a space velocity of 1200 hours -1 . The removal rate of lead is 30% or more. 一種濾材，其包含如請求項14至17中任一項之多孔質碳材料，於將含有0.2毫克/升游離氯之水於空間速度1200小時-1 下連續進行50小時通液時，游離氯之除去率為70%以上。A filter material comprising the porous carbon material according to any one of claims 14 to 17, which is capable of passing through a continuous flow of water containing 0.2 mg/liter of free chlorine at a space velocity of 1200 hours -1 for 50 hours. The removal rate is 70% or more. 一種濾材，其包含如請求項14至17中任一項之多孔質碳材料，於將含有以氯換算為130微克/升之總有機鹵素之水於空間速度1200小時-1 下連續進行5小時通液時，總有機鹵素之除去率為45%以上。A filter material comprising the porous carbon material according to any one of claims 14 to 17, which is continuously subjected to water for a period of 5 hours at a space velocity of 1200 hours -1 in a water containing a total organic halogen of 130 μg/liter in terms of chlorine. When the liquid is passed, the total organic halogen removal rate is 45% or more.
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JP6218355B2 (en) 2017-10-25
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KR20140005218A (en) 2014-01-14
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CN110395783A (en) 2019-11-01
TW201238652A (en) 2012-10-01
CN106111057B (en) 2019-04-05
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CN106111056B (en) 2019-04-05
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